Book of Abstracts - Bursa Teknik Üniversitesi

Transkript

Book of Abstracts
NCC6 - The 6th Catalysis Conference
April 27-30, 2016,
Bursa Technical University - Bursa / TURKEY
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Organizing Institutions & Sponsors
Bursa Teknik Üniversitesi / NCC6 - The 6th Catalysis Conference
Editör / Prof. Dr. H. Levent Hoşgün
Görsel Tasarım / Yakup Şahiner
ISBN / 978-605-9332-00-2
Basım Yılı ve Yeri / 1. Baskı; Nisan 2016, Star Matbaacılık / Bursa
Yapım / © 2016 Bursa Teknik Üniversitesi; Bu kitabın tüm yayın hakları Bursa Teknik Üniversitesi'ne aittir. Yazılı izin olmadan
kısmen ya da tamamen yeniden basılamaz.
Dağıtım / Bursa Teknik Üniversitesi - 152 Evler Mahallesi Eğitim Caddesi 1.Damla Sok.No:2/10 16330 Yıldırım/BURSA
Tel: + 90 224 300 32 32 Faks: + 90 224 300 32 09 [email protected] / www.btu.edu.tr
April 27-30, 2016, Bursa Technical University
3
Table of Contents
LECTURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
ORAL PRESENTATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
TERRALAB POSTER PRESENTATIONS 28/04/2016 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
POSTER PRESENTATIONS 29/04/2016 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Lectures (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Support Effect in Oxide Catalysis: C-H Bond Activation on Vanadia/Ceria Compared to
Vanadia/Silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Catalysis for bio-olefins production: from research to industrial application . . . . . . . . . . . 37
Synthesis-Structure-Performance Relationships for Heterogeneous Catalysts . . . . . . . . . 38
Hydrogenation and Hydrogenolysis Reactions Involved in Treatment of Water Contaminated
with Chlorinated Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Energy Intensified Reactor Design with Radio Frequency Heating . . . . . . . . . . . . . . . . . . 40
STRUCTURE-PERFORMANCE RELATIONSHIPS IN SUPPORTED METAL CATALYSTS WITH
IONIC LIQUID LAYER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Oral Presentations (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Catalytic Role of Pyrite on Hydrodesulfurization of Lignite and Asphaltite . . . . . . . . . . . . . 43
REDUCED GRAPHENE OXIDE (RGO) SUPPORTED Pt NANOPARTICLES: EFFECT OF
DIFFERENT REDUCING AGENTS ON RGO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Catalytic Tar Removal on Nickel-loaded Perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Ultrasound assisted biodiesel production in presence of dolomite catalyst . . . . . . . . . . . 46
Ruthenium(0) nanoparticles supported on xonotlite nanowire: a long-lived catalyst for
hydrolysis of ammonia-borane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Synthesis of STA/SBA-15 Catalysts for Ethyl Acetate Production and Characterizations of
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
INVESTIGATION OF CATALYST, REACTION CONDITIONS AND PROCESS DESIGN FOR
HYDROGEN PRODUCTION FROM STEAM REFORMING OF GLYCEROL . . . . . . . . . . . . . . . 49
4
Oxy-CO2 Reforming of Methane over Al2O3 Supported Nickel Catalysts prepared by
Deposition-Precipitation with urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Production of 5-Hydroxymethylfurfural by Catalytic Dehydration of
Fructose over SO4/La-TiO2-SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Catalytic performance of transition metal doped montmorillonite for
biomass hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Parametric investigation of glycerol reforming in a wall-coated microchannel reactor . . 54
BIODIESEL PRODUCTION FROM MODEL WASTE VEGETABLE OIL BY
USING ZIRCONIUM SULFATE CATALYST . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
ESTERIFICATION OF CETYL ALCOHOL AND PALMITIC ACID OVER W
AND Zr CONTAINING ACIDIC CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
DESIGN AND CHARACTERIZATION OF SELECTIVE CO2 ADSORBENTS . . . . . . . . . . . . . . . . 57
Novel Hybrid Perovskite Catalysts For DeNOx Applications . . . . . . . . . . . . . . . . . . . . . . . . 58
NH3 Uptake Behavior of a Commercial Cu-Zeolite Monolithic Catalyst
for the NH3-Selective Catalytic Reduction of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Sulfur-Tolerant BaO/ZrO2/TiO2/Al2O3 Quaternary Mixed Oxides for DeNOx Catalysis . . . . . 60
Development of CuOx/nr-TiO2 Catalysts for CO2 abatement . . . . . . . . . . . . . . . . . . . . . . . 62
Carbon Aerogel Supported Platinum-Copper Nanoalloys Using
Supercritical Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Enviromental Friendly Latent Ruthenium Metathesis Catalysts for
the Synthesis of Nano-ROMP Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
KINETIC AND MECHANISTIC FEATURES OF CARBON DIOXIDE
REFORMING OF METHANE OVER Co–Ce/ZrO2 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . 65
Computational (DFT) and Experimental (FTIR-DRIFT) Investigation of CO2
Activation on ZrO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
Performance test of monolithic Ni-based catalyts for carbon dioxide
reforming of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Structure-performance relationships in supported nickel catalysts for
hydrogen production from ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
The Effects of Reaction Parameters on Mn/Na2WO4/SiO2 Catalyst for
Oxidative Coupling of Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
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POSTER PRESENTATIONS (Abstracts) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Schiff Base complexes on bleach catalyst for the real industrial applications . . . . . . . . . 70
CHARACTERIZATION OF CATALYTIC CONVERTER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
POLYANILINE COATING ON MODIFIED CARBON PASTE ELECTRODE TO CONSTRUCT
AMPEROMETRIC GLUCOSE BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
THE USE OF CYCLIC ENONES AS ORGANIC MOLECULES TO CONSTRUCT OF
AMPEROMETRIC GLUCOSE BIOSENSORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
IMPROVEMENT OF GLUCOSE BIOSENSOR BY CATALYTIC EFFICIENCY OF ZnFe2O4
NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
GLUCOSE OXİDASE IMMOBILIZATION ON POLY(o-TOLUIDINE) COATED
Pt ELECTRODE FOR AMPEROMETRIC BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Double Catalytic Centers: Potential Therepautic Applications for the
Treatment of Oxidative Stress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
RESPONSE SURFACE METHODOLOGY FOR OPTIMIZATION OF CONSTRUCTION OF
AMPEROMETRIC GLUCOSE BIOSENSORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
THE CO-IMMOBILIZED ENZYME SYSTEM FOR LACTOSE SENSITIVE BIOSENSOR . . . . . . . 79
CARBON PASTE ELECTRODE BASED SUCROSE BIOSENSOR . . . . . . . . . . . . . . . . . . . . . . 80
GLUCONIC ACID PRODUCTION BY co-IMMOBILIZED GLUCOSE
OXIDASE-CATALASE ENZYME SYSTEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
N,O-type Schiff base ligands and transition metal complexes
containing functional groups: Structural Characterization and SOD Activity Studies . . . . . 82
Catalytic Conversion of Superoxide by Porphyrine Based Metal Complexes . . . . . . . . . . . 83
Porphyrine Based Mn(III) and Fe(III) Complexes as SOD Mimetics:
Subsituent Effects on Catalytic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Hydrolysis of microalgae oil Chlorella protothecoides via biocatalysis . . . . . . . . . . . . . . . 85
Immobilization and characterization of Candida rugosa lipase on
magnetic nanoparticles through different spacer arms . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Effect of Calcination Temperature on Production of DMN’s over Y Zeolite Catalyst . . . . . . 88
Methylation of Naphthalene Oil Fraction of Coal Tar with
Methanol on Metal/Bimetal Doped Beta Zeolite Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 89
MODIFICATION OF ACTIVATED CARBON BASED ADSORBENTS FOR CO2 ADSORPTION . . 90
ENHANCING PHOTOCATALYTIC ACTIVITY OF ZnO NANOROD WITH HEAT TREATMENT . . . 91
6
Low Platinum Loading Electrode for Formic Acid Fuel Cell Prepared by
Ion-Beam Assisted Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Pt Catalyst Supported on Bi2O3 for Direct Formic Acid Fuel Cells . . . . . . . . . . . . . . . . . . . 93
CATALYTIC GASIFICATION OF ÇAN LIGNITE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Ceria Incorporated Alumina Supported Nickel Catalysts for Steam
Reforming Reaction of Diesel Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
PtCu/C BIMETALLIC CATALYSTS FOR PEM FUEL CELLS . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Effects of Synthesis Route and Calcination Temperature on
Structural and Acidic Properties of Mesoporous -Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Effect of Marl on the Production of Biodiesel as a Heterogeneous Catalyst . . . . . . . . . . . 98
Hydrogen Production over Mesoporous Carbon Supported Iron Nanocatalysts using
Microwave Reactor system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
ELECTROCHEMICAL BEHAVIOUR OF HYBRID NANOSTRUCTURED
MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . 100
CARBON BLACK-GRAPHENE HYBRID SUPPORT MATERIALS FOR PEM FUEL CELL
ELECTROCATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
INFLUENCE OF TYPE OF CARBON SUPPORT ON THE REFORMING ACTIVITY AND
SELECTIVITY OF SUPPORTED Pt CATALYSTS FOR APR OF GLUCOSE . . . . . . . . . . . . . . . 102
CoRh NANOPARTICLES: SYNTHESIS, CHARACTERIZATION,
THEIR USE AS CATALYST IN THE HYDROLYSIS OF HYDRAZINE BORANE . . . . . . . . . . . . . 104
Ni(II) COMPLEX COVERED ZnO FILM OF PHOTOCATALYSTS
FOR EFFICIENT HYDROGEN PRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Pt Catalyst Supported on High Surface Area MCM-41 and its
Catalytic Activity for Formic Acid Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Development of Co-B/ Sepiolite Catalysts for Hydrogen
Generation by Hydrolysis of Sodium Borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
Oxygen reduction and oxygen evolution reaction performances of
PtNi/CuO catalyst for lithium-air batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Preparation of Ni Catalyst on Co3O4 Support Material for H2 Production . . . . . . . . . . . . . 110
Syntheses and Characterization of Ni Containing Silica Microspheres . . . . . . . . . . . . . 111
NEW DYE-SENSITIZIED Cu(I) COMPLEX PHOTOCATALYSTS BEHAVIOUR ON
PHOTOELECTROLYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
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THE CONVERSION OF CELLULOSE TO 5-HYDROXYMETHYL
FURFURAL (HMF) WITH ZEOLITE CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Oxidative Steam Reforming of Biogas by over NiCe/MgAl Hydrotalcite-like catalysts . . . 114
Microwave Assisted COx-free Hydrogen Production over
Mesoporous Carbon Supported Molybdenum Nanocatalysts . . . . . . . . . . . . . . . . . . . . . 115
HYDROGEN GENERATION FROM AMMONIA BORANE
HYDROLYSIS CATALYZED BY CoPd NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
EFFECT OF REACTION TEMPERATURE ON COKE
FORMATION IN DRY REFORMING OF METHANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
THE ROLE OF PRECIOUS METALS ON ADSORPTION/DESORPTION
KINETICS OF OXYGEN OVER REDUCIBLE OXIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
MODELING OF DATABASE CONSTRUCTED FROM PUBLISHED
ARTICLES FOR WATER SPLITTING OVER PEROVSKITES . . . . . . . . . . . . . . . . . . . . . . . . . 119
MORPHOLOGY OF PT-CU NANOPARTICLES BY USING
GENETIC ALGORITHM AND DENSITY FUNCTIONAL THEORY . . . . . . . . . . . . . . . . . . . . . . 120
TEMPERATURE EFFECT ON THE CARBON DIOXIDE SORPTION
CAPACITY OF NATURAL MAGNESITE DERIVED SORBENT . . . . . . . . . . . . . . . . . . . . . . . 121
PREPARATION SUPPORTED PT AND RU CATALYSTS AND
THEIR PERFORMANCES IN AVPR PROCESS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Investigation of Metal Loading Ratio Effect on
Characteristics of Co/Al2O3 Catalysts and Utilization in Catalytic Pyrolysis . . . . . . . . . . . 123
AN EFFICIENT HETEROGENEOUS CR-ZEOLITE CATALYST FOR GLUCOSE TO
5-HYDROXYMETHYLFURFURAL CONVERSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
N-HETEROCYCLIC CARBENE-BASED NICKEL(II) COMPLEXESIN KUMADA COUPLING . . . 125
Sorption Enhanced Steam Reforming of Ethanol Over Ni
Impregnated SBA-15 Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
ESTERIFICATION OF GLYCEROL WITH OLEIC ACID over
Ti CONTAINING SULFATED SBA-15 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Synthesis and Characterization of Perovskite Catalyst and Its
Catalytic Activity in Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
EPOXIDATION OF METHYL OLEATE OVER SO4/TiO2-SiO2 AND
WO3-ZrO2 CATALYSTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
THE EFFECT OF PEROXIDE ON BIOMASS HYDROLYSIS AND
CATALYTIC GASIFICATION OF HYDROLYSATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
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Palladium (0) Nanoparticles Supported on Amine-Functionalized
Silica for the Catalytic Hexavalent Chromium Reduction . . . . . . . . . . . . . . . . . . . . . . . . 131
PALLADIUM NANOPARTICLES(Pd NPs) AS EFFICIENT CATALYSTS
FOR SUZUKI-MIYAURA REACTION IN MILD CONDITIONS . . . . . . . . . . . . . . . . . . . . . . . . 132
Investigation of Isobutane Dehydrogenation in a Pd-membrane Reactor . . . . . . . . . . . . 133
PREPARATION OF NOVEL VIC-DIOXIME-Pd(II) COMPLEX FOR
SUZUKI-MIYAURA REACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
POTENTIAL APPLICATIONS OF SOLID SUPPORT CATALYTIC MEDICAL MOLECULAR . . . . 136
AMMONIA SYNTHESIS REACTION ON Ru NANOPARTICLES . . . . . . . . . . . . . . . . . . . . . . 137
ARTIFICIAL HUMAN BLOOD and Antioxidant Enzyme Catalysis:
Glutathione peroxidase, catalase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
Ruthenium Nanoparticles Stabilized Hidrotalcite Catalyst for the
Methanolysis of Ammonia-Borane under Mild Conditions . . . . . . . . . . . . . . . . . . . . . . . 139
Effect of Crystal Structure on the Catalytic Activity for Suzuki-Miyaura
Coupling Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
Sulfonic Acid Functionalized MIL-101 Metal Organic Framework Confined
Palladium(0) Nanoparticles Catalyst for the Methanolysis of
Ammonia-Borane under Mild Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
IMMOBILIZATION OF GLUTAMATE DEHYDROGENASE ONTO AMINATED
CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY . . . . . . . . . . . . . . . . . 142
IMMOBILIZATION OF XANTHINE OXIDASE ONTO AMINATED CARBON
NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY AND STABILIZATION . . . . . . . . . 143
THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR
ACCUMULATION OF IRON IN THE BODY ON GLUTATATHIONE PEROXIDASE ENZYME . . . . 144
THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE USED FOR
ACCUMULATION OF IRON IN THE BODY ON XANTHINE OXIDASE ENZYME . . . . . . . . . . . 145
PREPARATION AND APPLICATION OF AlK(SO4)2.12H2O LOADED CHITOSAN/
POLYVINYLPYRROLIDONE CATALYTIC MEMBRANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
PHOSPHOTUNGSTIC ACID LOADED CELLULOSE MEMBRANE
PREPARATION FOR CATALYTIC MEMBRANE REACTOR . . . . . . . . . . . . . . . . . . . . . . . . . 147
Palladium(II)-Schiff base complex supported on mwcnt for using as
catalyst in the Suzuki-Miyaura reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
9
Metal Organic Framework (MIL-101) Stabilized Ruthenium(0)
Nanoparticles: Highly Efficient Catalytic Material for the Selective
Hydrogenation of Phenol to Cyclohexanone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Trimetallic PdAuNi Alloy Nanoparticles Supported on Amine Functionalized Reduced
Graphene Oxide for the Dehydrogenation of Formic Acid Under Mild Conditions . . . . . . 151
Synthesis and insitu catalytic aplication of 7-BER-NHC ligands on Suzuki reaction . . . . 152
Improvement of Sulfur Regenaration Ability of NSR Catalysts via Reducible
Mixed Oxide Promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Selective CO2 adsorption studies on NaOH impregnated AC Adsorbents . . . . . . . . . . . . 155
Spectroscopic Investigation of NOx Storage and Reduction
Pathways on Pt/K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts . . . . . . . . . . . . . . . . . . . . . . 156
Removing of Synthetic Dyes from Aqueous Solutions By Using Photocatalysis and
Adsorption Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
ANODIC BEHAVIOR OF CARBON SUPPORTED Ni-Co, Ni AND Co
ELECTROCATALYST IN DIRECT BOROHYDRIDE FUEL CELL . . . . . . . . . . . . . . . . . . . . . . . 159
THE POLYANILINE FILMS on ZnNi PLATED COPPER ELECTRODE . . . . . . . . . . . . . . . . . . 160
Mn3O4 BASED ELECTROCATALYST SYNTHESIS FOR VANADIUM REDOX
FLOW BATTERIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Synthesis, Characterization and Photocatalytic Performance of Ag\ZnO in the
Photodegradation of Methylene Blue under UV Irradiation . . . . . . . . . . . . . . . . . . . . . . 162
SYNTHESIS OF CNT-TiO2-SiO2 NANOCOMPOSITE THIN FILMS: THE EFFECT OF HEAT
TREATMENT ON PHOTOCATALYTIC ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
Determination of Reaction Kinetics for Electrochemical Oxidation of
Tetracycline Antibiotic using Boron-Doped Diamond Anode . . . . . . . . . . . . . . . . . . . . . . 164
THE ELECTROCATALYTIC BEHAVIOR OF COPOLYMER FILMS ON ZnFeCo DEPOSITED
CARBON STEEL ELECTRODE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
ELECTROCATALYTIC CONDUCTING POLYMER FILMS ON Zn DEPOSITED CARBON STEEL
ELECTRODE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
COBALT-BASED COORDINATION COMPOUNDS FOR ELECTROCATALYTIC
WATER OXIDATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
Determination of optimum Cu-CeO2 ANODE composition for direct methane solid
oxide fuel cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
Characterization of PAni-Fe Electrocatalyst Loaded on Multi-walled Carbon Nanotube
Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
10
Benzene Oxidation as an Alternative Method for Assessing Photocatalytic Activity . . . . . 171
Synthesis, Characterization and Catalytic Activityin The Direct Arylation Reactions . . . . 173
SYNTHESIS STUDIES OF THE PROMISING CATALIST; MIL-101 . . . . . . . . . . . . . . . . . . . . 174
Synthesis of Chiral Catalysts and Their Catalytic Activities in ScCO2 . . . . . . . . . . . . . . . 175
GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE CATALYZED BY PVP, Al2O3AND
PS-co-MASTABILIZED Ru NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
Catalytic applications andsynthesis of Pd-PEPPSI
N- Heterocyclic Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
Synthesis of poly(cyclooctene) derivatives bearing imidazole end group by ROMP
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
Direct Arylation with Palladium-NHC Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Magnetic Nanoparticle Supported Latent Ruthenium Metathesis Catalysts for Olefin
Metathesis Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Modification of Functional Polyesters by Metathesis Reactions in the Presence of HoveydaGrubbs Type Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Synthesis of Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 Type Nanocomposite Catalystsfor Vitamin K3
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
Modification of Poly(norbornenediester) Derivatives with Primary and Secondary Amine
Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Reusability of nano-12-tungstophosporic acid cesium salt in alkylation of benzene with
dec-1-ene reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Alumina Supported Mn-Ce Sorbents for High Temperature Desulfurization of Hydrogen
Rich Gas Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Catalytic Wet Peroxide Oxidation of Bisphenol A in Water . . . . . . . . . . . . . . . . . . . . . . . 186
Graphene Supported Aminomethylphosphine-Pd(II) and Pt(II) Complexes: Highly Efficient
Catalysts on Vitamin K3 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
N-Alkylation Reaction with Functionalized Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . 189
The Coupling Reaction With Aryl Grignard Reagents in the Presence of
Iron/NHC Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
Palladium-NHC Complex Catalyzed Cross Coupling Reactions . . . . . . . . . . . . . . . . . . . . 191
PHOTOCATALYTIC WATER SPLITTING OVER Au/SrTiO3CATALYST . . . . . . . . . . . . . . . . . . . 192
IN SITU GENERATION COPPER(0) NPs AND CONCOMITANT GREEN DEHYDROGENATION OF
DIMETHYLAMINE-BORANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
11
Synthesis of Palladium(II) Schiff Base Complex And it’s Catalytic Activities C-C Coupling
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
HYDROBENZOIN TYPE LIGANDS FOR ASYMMETRIC CATALYSIS . . . . . . . . . . . . . . . . . . . 195
THE SYNTHESIS OF MAGNETIC NANOPARTICLES SUPPORTED AZOMETHINE-OXIME-PD
COMPLEX AND ITS CATALYTIC ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
N-Substitutedbenzimidazole-Ruthenium(II) Complexes and Their Catalytic Activity . . . . 197
Determination of Radiation Absorption Properties of Gamma Irradiated Polyoxovanadate
Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
EFFECTS OF THE PREPARATION METHOD AND CALCINATION TEMPERATURE ON THE
CHARACTERISTIC PROPERTIES OF NiO-Fe2O3-SiO2 CATALYSTS . . . . . . . . . . . . . . . . . . . 199
Modular Ligands Allowing Tunable Steric and Electronic Effects for Transition Metal
Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Synthesis of Tungstophosphoric Acid Incorporated Mesoporous Alumina Catalysts for
Methanol Dehydration in DME Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Production of 2,6-Dimethylnaphthalene with Methylation of Naphthalene over
Au/Mordenite Zeolite Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
CHARACTERIZATION OF Ni/ZrTiO4CATALYSTFOR THE PARTIAL OXIDATION of METHANE . 204
Characterization and Catalytic Performance of MnxOy-Na2WO4/SiO2 for the Oxidative
Coupling of Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
The Effect of Metal Adding Sequence and Synthesis Media on the
Properties of SnSBA-15 Catalysts at Low Metal Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . 206
Effect of Ti-Ce Contenton the Catalytic Activity of Alumina Supported
Catalysts in Selective Oxidation of H2S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
INVESTIGATION and CHARACTERIZATION of Ni/MgO CATALYST PREPARED BY
ELECTROSPINNIG TECHNIQUE for the PARTIAL OXIDATION and DRY REFORMING of
METHANE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
THE CATALYTICACTIVITY OF AZO CONTAINING SCHIFF BASE COMPLEXES . . . . . . . . . . . 211
TRANSITION METAL COMPLEXES OF NOVEL CHROMONE SCHIFF BASES: SYNTHESIS,
CHARACTERIZATION AND CATECHOLASE-LIKE ACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . 212
Hydrothermal Synthesis and Characterization of Heterogeneous
Catalysts for the Oxidation of the Thymol To Thymoquinone . . . . . . . . . . . . . . . . . . . . . 214
SUITABLE CATALYST OBTAINING FOR ALKANE OXIDATION AND ALKENE EPOXIDATION
REACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
POLYMER SOLID SUPPORT CATALYSTS FOR ALKANE OXIDATION . . . . . . . . . . . . . . . . . . 216
12
CATALYST DESIGN FOR ALKENE EPOXIDATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
New Ferrocene Based Schiff Bases Metal Complexes: Synthesis and Investigation of
Catalytic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Oxidation of alkanes with hydrogen peroxide catalyzed by ferrocene . . . . . . . . . . . . . . 220
Transition Metal Complexes of Ligand in a Liquid Crystal Properties: Investigation of the
Catalytic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Novel Gallic Esters: Its Synthesis, Structural Characterization, Photoluminescence,
Electrochemical Properties And Alkene Epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Catalytic activity of Schiff Base Mn(III)/Co(III) complexes on bleach catalyst . . . . . . . . . . 223
Catalytic Oxidation of Nitrogen Containing Compounds for Nitrogen Determination . . . . 224
Catalytic Properties of ONO Type Salicylaldimine Copper(II) Complexes . . . . . . . . . . . . 225
Copper Complexes with Bidentate NO Ligands as Novel Catalysts for the Homogeneous
Partial Oxidation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
The comparison of catalytic activity of non-ionic and ionic Mn(III)/Co(II) Phthalocyanine
complexes on bleach systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
THE CATALYTIC ACTIVITY OF NOVEL, AZO-CONTAINING SCHIFF BASES
AND THEIR METAL COMPLEXES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Investigation of Oxidation Reaction Pathways of Oxygenates on Au(111) Single
CrystalDepending on the Behaviour of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Effective Catalysts Derived from Carbazole for Alkene oxidation . . . . . . . . . . . . . . . . . . 230
Schiff base transition metal complexes with ceftazidime: Synthesis and
Investigation of Alkane Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Drug metal complexes: Synthesis and Investigation of Alkane Oxidation . . . . . . . . . . . . 232
Synthesis and Characterization of MCM-41 Supported Ni Catalysts for
Acetic Acid Steam Reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
COMPARISON OF FRESH FCC CATALYSTS, E-CAT SAMPLES and FCC ADDITIVES FOR
COMPREHENSION OF THE PROCESS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
Hydrogen Adsorption on M2+-LTL Zeolite Clusters (M = Be, Mg and Ca) : A Density
Functional Theory Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Investigation of Surface Acidity of Metal/Bimetal Modified Zeolite
Catalysts using Pyridine Probe Molecule by FT-IR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
Synthesis and Characterization of CMK-3 and Activated Carbon Based Catalysts . . . . . 237
IMPACT OF HYDROCRACKING CATALYST CHARACTERISTICS ON THE
13
PERFORMANCE OF HYDROCRACKING UNIT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
AMMONIA DECOMPOSITION REACTION OVER ZEOLITE Y SUPPORTED IRON CATALYSTS:
EFFECT OF DEALUMINATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Palladium (II) Schiff Base Complexes: Precursor for the Deposition onto
the mesoporous SBA-15 in scCO2 Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Synthesis and Characterization of SBA15 Mesoporous Materials
Functionalized with Boron Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Determination of ΔH°, ΔS° and ΔG° valuesof B-SBA15 Mesoporous
Materials Using InverseGasCromatographyTechnique . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Single Step Synthesis of HPA loaded Al-PILCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Zeolite Catalysis for Bio-oil Upgrading via Esterification . . . . . . . . . . . . . . . . . . . . . . . . 244
14
Dear Colleagues of Universal Catalysis Community,
We are honored to welcome you to the NCC6-The 6th Catalysis Conference in Turkey.
On behalf of the Organization Committee, it is my privilege to extend our regards to all
our invited lecturers and the participants which will share their special scientific findings
and high academic knowledge, in the ever expanding world of catalyst.
I would like to commence by quoting some specific numbers to give a broad picture
of the status of the NCC6. The number of abstracts submitted, rose to about 184;
approximately 27 oral presentations have been scheduled, together with 157 posters.
We will have the opportunity to listen to about six Invited and Pleanary Talks in this
meeting, including our world-renowned Plenary and Invited Speakers: Prof. Dr. Joachim
Sauer (EFCATS Francois Gault Lecture, Humboldt University), Prof. Dr. Krjin De Jong
(Utrecht University), Prof. Dr. Ümit Özkan (Ohio State Univeristy), Prof. Dr. Fabrizio
Cavani (Bologna University), Volkan Değirmenci (University of Warwick) and Alper
Uzun (Koç University)
The NCC6 acquired the efforts of many people and the support from a number of
parties. The Chairs of NCC6 –Catalysis Society of Turkey, Organizing Committee,
Scientific Committee and Reviewers – were involved in the organization and devoted
their time and talent. I have only praise for their dedication to make the NCC6 a worldclass event. To all of my fellows in this organization, our most sincere recognition and
gratefulness.
The NCC6 has benefited from many sponsors. Their support of the congress as a whole
is duly appreciated. Particularly, we would like to thank TUBITAK (The Scientific and
Technological Research Council of Turkey), BTSO (Bursa Chamber of Commerce and
Industry), Bursa Metropolitan Municipality and TUPRAS A.Ş for their great support.
I wish you all, a fruitful and rewarding experience at NCC6. We are in anticipation
that NCC6 will provide a versatile platform for formal and informal discussions with
colleagues both from academia and industry and foster new visions of collaborations.
On the Behalf of Organizing Committee
Prof. Dr. M. Ali Gürkaynak
Chairman
15
Committes
Honorary Board
Prof. Dr. Mahmut Ak
Prof. Dr. Arif Karademir
Prof. Dr. Timur Doğu
Prof. Dr. Zeynep İlsen Önsan
Recep Altepe
Rector of İstanbul University
Rector of Bursa Technical University
Middle East Technical University
Mayor of Metropolitan Municipality
Scientific Committee
Prof. Dr. Mehmet Ali Gürkaynak
Prof. Dr. Mehmet Çopur
Prof. Dr. J W (Hans) Niemantsverdriet
Prof. Dr. Jens Rostrup-Nielsen
Prof. Dr. Mahmut Bayramoğlu
Prof. Dr. Gülşen Doğu
Prof. Dr. Xenophon Verykios
Prof. Dr. Deniz Üner
Prof. Dr. R.A. (Rutger) van Santen
Prof. Dr. Can Erkey
Prof. Dr. Ramazan Yıldırım
Prof. Dr. Maria Flytzani-Stephanopoulos
Prof. Dr. Enrique Iglesia
Prof. Dr. Bilgehan Güzel
Prof. Dr. Ayşe Nilgün Akın
Prof. Dr. Ahmet Erhan Aksoylu
Prof. Dr. Martin Muhler
Prof. Dr. Suna Balcı
Prof. Dr. Süheyda Atalay
Prof. Dr. Selahattin Yılmaz
Prof. Dr. Matthias Beller
Assoc. Prof. Ahmet Kerim Avcı
Assoc. Prof. M. Ali Faruk Öksüzömer
Assoc. Prof. Serkan Naci Koç
Dr. Daniele Toffoli
İstanbul University, Turkey
Bursa Technical University, Turkey
Director Syngaschem BV, Beijing
Haldor Topsøe A/S, Denmark
Gebze Technical University, Turkey
Gazi University, Turkey
University of Patras, Greece
Middle East Technical University, Turkey
Eindhoven of University,Netherlands
Koç University, Turkey
Boğaziçi University, Turkey
University of Tufts, USA
University of California, Berkeley, USA
Çukurova University, Turkey
Kocaeli University, Turkey
Ruhr-Universitat Bochum, Germany
Gazi University, Turkey
Ege University, Turkey
İzmir High Technology Institute, Turkey
Leibniz-Institute for Catalysis, Germany
University of Trieste, Italy
16
Organizing Committee
Prof. Dr. Mehmet Ali Gürkaynak
Prof. Dr. Mehmet Çopur
Assoc. Prof. Dr. M. Ali Faruk Öksüzömer
Assoc. Prof. Dr. Emrah Özensoy
Assoc. Prof. Dr. Mehmet Ferdi Fellah
Assist. Prof. Dr. Tuba Gürkaynak Altınçekiç
Assist. Prof. Dr. H. Levent Hoşgün
İstanbul University
Bursa Technical University
Bilkent University
Catalysis Society of Turkey Executive Board
Prof. Dr. Z. İlsen Önsan
Boğaziçi University
Cantaş Öğülmüş
Damla Kimya
Assoc. Prof. Dr. Alper Tapan
Gazi University
Bilkent University
Assist. Prof. Dr. Alper Uzun
Koç University
Prof. Dr. İsmail Özdemir
İnönü University
Reviewers
Prof. Dr. Ahmet Erhan Aksoylu
Prof. Dr. Can Erkey
Prof. Dr. Ayşe Nilgün Akın
Assoc. Prof. Dr. Ahmet Kerim Avcı
Assoc. Prof. Dr. M. Ali Faruk Öksüzömer
Assoc. Prof. Dr. Serkan Naci Koç
Assoc. Prof. Dr. Mehmet Ferdi Fellah
Assist. Prof. Dr. H. Levent Hoşgün
Assist. Prof. Dr. Solmaz Akmaz
Koç University
Kocaeli University
Bilkent University
17
LECTURES
L1
L2
L3
L4
L5
L6
TITLE
AUTHOR(S)
Support Effect in Oxide Catalysis:C-H Bond Prof. Dr. Joachim Sauer, (EFCATS Francois
Activation on Vanadia/Ceria Compared to Gault Lecture)
Vanadia/Silica
Humboldt University, Berlin
Catalysis for bio-olefins production: from Prof. Dr. Fabrizio Cavani,
research to industrial application
Bologna University ,Industrial Chemistry
S y n t h e s i s - S t r u c t u r e - P e r f o r m a n c e Prof. Dr. ir. K.P. (Krijn) de Jong,
Relationships for Heterogeneous Catalysts
Utrecht University, Inorganic Chemistry and
Catalysis
Hydrogenation
and
Hydrogenolysis Prof. Dr. Ümit Özkan,
Reactions Involved in Treatment of
Ohio State Univeristy , Chemical &
Water Contaminated with Chlorinated
Biomolecular Eng.
Hydrocarbons
Energy Intensified Reactor Design with Dr. Volkan Değirmenci,
Radio Frequency Heating
University of Warwick, School of
Engineering
Structure-Performance Relationships In Assist. Prof. Dr. Alper Uzun,
Supported Metal Catalysts With Ionic Liquid
Koç University, Chemical & Biological
Layer
Engineering
18
ORAL PRESENTATIONS
Catalysts for coal based chemicals
TITLE
O-CBC1
Catalytic
Role
of
Hydrodesulfurization of
Asphaltite
AUTHOR(S)
Pyrite
Lignite
on Veysi Halvaci, Arzu Kanca, Deniz Uner
and
Catalysts for sustainable energy and alternative fuels
TITLE
AUTHOR(S)
O-SEAF1
REDUCED GRAPHENE OXIDE (RGO) Elif DAŞ, Ayşenur ÖZTÜRK,
SUPPORTED Pt NANOPARTICLES: EFFECT BAYRAKÇEKEN YURTCAN
OF DIFFERENT REDUCING AGENTS ON
RGO
Ayşe
O-SEAF2
Catalytic Tar Removal on Nickel-loaded Basar Caglar, Taymaz Tabari, Deniz Üner
Perovskites
O-SEAF3
Ultrasound assisted biodiesel production İbrahim Korkut, Mahmut Bayramoğlu
in presence of dolomite catalyst
O-SEAF4
Ruthenium(0) nanoparticles supported on Serdar Akbayrak, Saim Özkar
xonotlite nanowire: a long-lived catalyst
for hydrolysis of ammonia-borane
O-SEAF5
Synthesis of STA/SBA-15 Catalysts Veli SIMSEK, Kirali MURTEZAOGLU
for Ethyl Acetate Production and
Characterizations of Catalysts
O-SEAF6
INVESTIGATION OF CATALYST, REACTION Öykü Parlar, M. Efgan Kibar, A. Nilgün Akın,
CONDITIONS AND PROCESS DESIGN FOR Meltem Karaman
HYDROGEN PRODUCTION FROM STEAM
REFORMING OF GLYCEROL
O-SEAF7
OXY-CO2 REFORMING OF METHANE Tuba Gürkaynak Altınçekiç, Tugay Pehlivan
SUPPORTED
NICKEL
OVER Al2O3
CATALYSTS PREPARED BY DEPOSITIONPRECIPITATION WITH UREA
Catalytic Conversion of renewable resources
TITLE
AUTHOR(S)
O-CRS1
PRODUCTION
OF Emre KILIÇ, Tjeerd Alexander NIJHUIS,
5-HYDROXYMETHYLFURFURAL
BY Selahattin YILMAZ
CATALYTIC DEHYDRATION OF FRUCTOSE
OVER SO4/La-TiO2-SiO2
O-CRS2
Catalytic performance of transition metal Emir Zafer Hoşgün, Ebru Tunç, Halit Levent
doped montmorillonite for biomass Hoşgün, Berrin Bozan
hydrolysis
19
O-CRS3
Parametric investigation of glycerol Sinan Koc, Ahmet Kerim Avci
reforming in a wall-coated microchannel
reactor
O-CRS4
BIODIESEL PRODUCTION FROM MODEL Melike İmge ŞENOYMAK, Oğuzhan İLGEN
WASTE VEGETABLE OIL BY USING
ZIRCONIUM SULFATE CATALYST
O-CRS5
ESTERIFICATION OF CETYL ALCOHOL Vahide Nuran Mutlu, Selahattin YILMAZ
AND PALMITIC ACID OVER W AND Zr
CONTAINING ACIDIC CATALYSTS
Catalytic methods for air water pollution control
TITLE
AUTHOR(S)
O-AWPC1 DESIGN AND CHARACTERIZATION OF Burcu Acar, Burcu Selen Çağlayan, A.
Erhan Aksoylu
SELECTIVE CO2 ADSORBENT
O-AWPC2 Novel Hybrid Perovskite Catalysts For K.E. Ercan, Z. Say, E.I. Vovk, G. Pantaleo, L.
Liotta, A. Venezia, and E. Ozensoy
DeNOx Applications
O-AWPC3 NH3 Uptake Behavior of a Commercial Selmi Erim Bozbağ, Feyza Gökaliler,
Cu-Zeolite Monolithic Catalyst for the NH3- Gökhan Hisar, Can Erkey
Selective Catalytic Reduction of NOx
O-AWPC4 Sulfur-Tolerant
BaO/ZrO2/TiO2/Al2O3 Z. Say, O. Mihai, M. Tohumeken, L. Olsson,
Quaternary Mixed Oxides for DeNOX E. Ozensoy
Catalysis
Electrochemical and photochemical catalysts
TITLE
AUTHOR(S)
O-EPC1
Development of CuOx/nr-TiO2 Catalysts for Murat Efgan KİBAR, Gizem GÜRGÜR, Ayşe
CO2 abatement
Nilgün AKIN
O-EPC2
Carbon Aerogel Supported Platinum- Şansım Bengisu BARIM, Ezgi Erdem, Selmi
Copper Nanoalloys Using Supercritical Erim Bozbağ, Rıza Kızılel, Mark Aindow,
Haibo Yu, Can Erkey,
Deposition
Environmentally friendly catalytic processes
TITLE
AUTHOR(S)
O-EFCP1
Enviromental Friendly Latent Ruthenium Bengi Özgün ÖZTÜRK, Solmaz KARABULUT
Metathesis Catalysts for the Synthesis of ŞEHİTOĞLU
Nano-ROMP Polymers
O-EFCP2
KINETIC AND MECHANISTIC FEATURES Aysun İpek Paksoy, Cansu Yassı Akdağ,
OF CARBON DIOXIDE REFORMING OF Burcu Selen Çağlayan, A. Erhan Aksoylu
METHANE OVER Co–Ce/ZrO2 CATALYSTS
O-EFCP3
Computational (DFT) and Experimental A. Uzun, A. İ. Paksoy, V. Çimenoğlu, A. E.
(FTIR-DRIFT) Investigation of CO2 Aksoylu
Activation on ZrO2
20
O-EFCP4
Performance test of monolithic Ni-based Aybüke Leba, Ramazan Yıldırım
catalyts for carbon dioxide reforming of
methane
O-EFCP5
Structure-performance relationships in İbrahim Şahin, Alper Uzun
supported nickel catalysts for hydrogen
production from ammonia
Oxidation catalysts
TITLE
AUTHOR(S)
O-OXC1
The Effects of Reaction Parameters on Hasan Özdemir, M.A. Faruk Öksüzömer, M.
Mn/Na2WO4/SiO2 Catalyst for Oxidative Ali Gürkaynak
Coupling of Methane
O-OXC2
Schiff Base complexes on bleach catalyst Ertug Yildirim,S. Zeki Yildiz, Okan Yuzuak,
Idil Yilmaz Yalinalp, Nihat Toslu
for the real industrial applications
O-OXC3
CHARACTERIZATION
CONVERTER
OF
CATALYTIC Yiğit Türe, Emre Gürlek, Nurcan Çalış
Açıkbaş, Şeref Soylu and Türker Güdü
21
TERRALAB POSTER PRESENTATIONS 28/04/2016
Biocatalysts
TITLE
AUTHOR(S)
BC1
POLYANILINE COATING ON MODIFIED A. Ebru AYDIN, Gul OZYILMAZ, Serbay
CARBON
PASTE
ELECTRODE TO BUCAK, Nureddin ÇOLAK, Ali Tuncay
CONSTRUCT AMPEROMETRIC GLUCOSE OZYILMAZ
BIOSENSOR
BC2
THE USE OF CYCLIC ENONES AS ORGANIC Gul OZYILMAZ, A. Ebru AYDIN, Serbay
MOLECULES TO CONSTRUCT OF Bucak, Seda AGCAM, Ali Tuncay OZYILMAZ
AMPEROMETRIC GLUCOSE BIOSENSORS
BC3
IMPROVEMENT OF GLUCOSE BIOSENSOR Ali Tuncay OZYILMAZ, Esiye İrem BAYRAM
BY CATALYTIC EFFICIENCY OF ZnFe2O4 and Gul OZYILMAZ
NANOPARTICLES
BC4
GLUCOSE OXİDASE IMMOBILIZATION Ali Tuncay OZYILMAZ, Esiye İrem BAYRAM
ON POLY(o-TOLUIDINE) COATED Pt and Gul OZYILMAZ
ELECTRODE
FOR
AMPEROMETRIC
BIOSENSOR
BC5
Double Catalytic Centers: Potential Ferhan Tümer, Songül Şahin, Mehmet
Therepautic Applications for the Treatment Tümer, Muhammet Köse
of Oxidative Stress
BC6
RESPONSE SURFACE METHODOLOGY FOR Gul OZYILMAZ, Seda AGCAM and Ali
OPTIMIZATION OF CONSTRUCTION OF Tuncay OZYILMAZ
AMPEROMETRIC GLUCOSE BIOSENSORS
BC7
THE CO-IMMOBILIZED ENZYME SYSTEM Esra YAĞIZ, Gul OZYILMAZ and Ali Tuncay
OZYILMAZ
FOR LACTOSE SENSITIVE BIOSENSOR
BC8
CARBON PASTE ELECTRODE
SUCROSE BIOSENSOR
BC9
GLUCONIC ACID PRODUCTION BY co- Gul OZYILMAZ
IMMOBILIZED
GLUCOSE
OXIDASECATALASE ENZYME SYSTEM
BC10
N,O-type Schiff base ligands and transition İlyas GÖNÜL, Muhammet KÖSE, Selahattin
metal complexes containing functional SERİN
groups: Structural Characterization and
SOD Activity Studies
BC11
Catalytic Conversion of Superoxide by Muhammet Köse, Ferhan Tümer, Mehmet
Tümer
Porphyrine Based Metal Complexes
BASED Esra YAĞIZ, Gul OZYILMAZ, and Ali Tuncay
OZYILMAZ
22
BC12
Porphyrine Based Mn(III) and Fe(III) Mehmet Tümer, Ferhan Tümer, Muhammet
Complexes as SOD Mimetics: Subsituent Köse
Effects on Catalytic Activity
BC13
Hydrolysis of microalgae oil Chlorella Togayhan Kutluk, Nurcan Kapucu
protothecoides via biocatalysis
BC14
Immobilization and characterization Muge SENGUL, Leman BEYKAN, Deniz
of Candida rugosa lipase on magnetic YILDIRIM, Guzide YUCEBILGIC
nanoparticles through different spacer
arms
Catalysts for coal based chemicals
TITLE
AUTHOR(S)
CBC1
Effect of Calcination Temperature on Aysel Niftaliyeva, Ali Karaduman
Production of DMN’s over Y Zeolite Catalyst
CBC2
Methylation of Naphthalene Oil Fraction of Aysun Özen, Fatih Güleç, Aysel Niftaliyeva,
Coal Tar with Methanol on Metal/Bimetal Ali Karaduman
Doped Beta Zeolite Catalysts
CBC3
MODIFICATION OF ACTIVATED CARBON Melek Selcen BAŞAR, Burcu SELEN
BASED
ADSORBENTS
FOR
CO2 ÇAĞLAYAN, Ahmet Erhan AKSOYLU
ADSORPTION
Catalysts for sustainable energy and alternative fuels
TITLE
AUTHOR(S)
SEAF1
ENHANCING PHOTOCATALYTIC ACTIVITY Fatih TEZCAN, Gülfeza KARDAŞ
OF ZnO NANOROD WITH HEAT TREATMENT
SEAF2
Low Platinum Loading Electrode for M. Selim ÇÖGENLİ, Sanjeev MUKERJEE,
Formic Acid Fuel Cell Prepared by Ion- Ayşe BAYRAKÇEKEN YURTCAN
Beam Assisted Deposition
SEAF3
Pt Catalyst Supported on Bi2O3 for Direct M. Selim ÇÖGENLİ, Ayşe BAYRAKÇEKEN
Formic Acid Fuel Cells
YURTCAN
SEAF4
CATALYTIC GASIFICATION OF ÇAN LIGNITE Açelya Seçer Ateş, Arif Hasanoğlu
SEAF5
Ceria Incorporated Alumina Supported Arzu Arslan, Arife Derya Deniz Kaynar,
Nickel Catalysts for Steam Reforming Naime Aslı Sezgi, Timur Doğu
Reaction of Diesel Fuel
SEAF6
PtCu/C BIMETALLIC CATALYSTS FOR PEM Ayşenur ÖZTÜRK, Elif DAŞ, Gamze
BOZKURT, Ayşe BAYRAKÇEKEN YURTCAN
FUEL CELLS
SEAF7
Effects of Synthesis Route and Calcination D. Erkal, B. Pekmezci, N. Oktar, G. Doğu,
Temperature on Structural and Acidic N.A. Sezgi, T. Doğu
Properties of Mesoporous γ-Al2O3
SEAF8
Effect of Marl on the Production of Bakhtiyar NAJAFOV, Niyazi Alper TAPAN
Biodiesel as a Heterogeneous Catalyst
23
SEAF9
Hydrogen Production over Mesoporous C.Korkusuz, D.Varışlı, T.Doğu
Carbon Supported Iron Nanocatalysts
using Microwave Reactor system
SEAF10
ELECTROCHEMICAL BEHAVIOUR OF Elif DAŞ, Selmiye ALKAN GÜRSEL, Lale
HYBRID NANOSTRUCTURED MATERIALS IŞIKEL ŞANLI, Ayşe BAYRAKÇEKEN
FOR PEM FUEL CELL ELECTROCATALYSTS YURTCAN
SEAF11
CARBON BLACK-GRAPHENE HYBRID Elif DAŞ, Selmiye ALKAN GÜRSEL, Lale
SUPPORT MATERIALS FOR PEM FUEL IŞIKEL ŞANLI, Ayşe BAYRAKÇEKEN
YURTCAN
CELL ELECTROCATALYSTS
SEAF12
INFLUENCE OF TYPE OF CARBON Burçak Kaya Özsel, Bahar Meryemoğlu,
SUPPORT ON THE REFORMING ACTIVITY Mehtap Kurtuluş, Arif Hasanoğlu, Sibel
AND SELECTIVITY OF SUPPORTED Pt Irmak
CATALYSTS FOR APR OF GLUCOSE
SEAF13
CoRh NANOPARTICLES: SYNTHESIS, Bayram Abay, Nihat Tunç, Murat Rakap
CHARACTERIZATION, THEIR USE AS
CATALYST IN THE HYDROLYSIS OF
HYDRAZINE BORANE
SEAF14
Ni(II) COMPLEX COVERED ZnO FILM Eylül Büşra HEREYTANİ, Fatih TEZCAN,
OF PHOTOCATALYSTS FOR EFFICIENT Bilgehan GÜZEL, Gülfeza KARDAŞ, Osman
SERİNDAĞ
HYDROGEN PRODUCTION
SEAF15
Pt Catalyst Supported on High Surface Niyazi ÖZÇELİK, M. Selim ÇÖGENLİ, Ayşe
Area MCM-41 and its Catalytic Activity for BAYRAKÇEKEN YURTCAN
Formic Acid Oxidation
SEAF16
Development of Co-B/ Sepiolite Catalysts Seda EROL, Mine ÖZDEMİR
for Hydrogen Generation by Hydrolysis of
Sodium Borohydride
SEAF17
Oxygen reduction and oxygen evolution Gamze BOZKURT, Tansel ŞENER, Dino
reaction performances of PtNi/CuO TONTI, A. Kadir ÖZER, Ayşe BAYRAKÇEKEN
YURTCAN
catalyst for lithium-air batteries
SEAF18
Preparation of Ni Catalyst on Co3O4 Gamze BOZKURT, Ayşe BAYRAKÇEKEN
Support Material for H2 Production
YURTCAN, A. Kadir ÖZER
SEAF19
Syntheses and Characterization of Ni Gamze Gunduz Meric, Levent Degirmenci
Containing Silica Microspheres
SEAF20
NEW DYE-SENSITIZIED Cu(I) COMPLEX Gurbet YERLİKAYA, Fatih TEZCAN, Gülfeza
PHOTOCATALYSTS
BEHAVIOUR
ON KARDAŞ, Osman SERİNDAĞ
PHOTOELECTROLYSIS
SEAF21
THE CONVERSION OF CELLULOSE TO Esra Sezgin, Merve Esen, Solmaz Akmaz,
5-HYDROXYMETHYL FURFURAL (HMF) Serkan Naci Koç, M. Ali Gürkaynak
WITH ZEOLITE CATALYSTS
SEAF22
Oxidative Steam Reforming of Biogas by Merve Doğan, Orhan Özcan, Murat Efgan
over NiCe/MgAl Hydrotalcite-like catalysts Kibar, Ayşe Nilgün Akın
24
SEAF23
Microwave Assisted COx-free Hydrogen Melih GÜLER, Dilek VARIŞLI, Timur DOĞU
Production over Mesoporous Carbon
Supported Molybdenum Nanocatalysts
SEAF24
HYDROGEN GENERATION FROM AMMONIA Nihat Tunç, Bayram Abay, Murat Rakap
BORANE HYDROLYSIS CATALYZED BY
CoPd NANOPARTICLES
SEAF25
EFFECT OF REACTION TEMPERATURE ON Hüseyin Arbağ, Sena Yaşyerli, Nail Yaşyerli,
COKE FORMATION IN DRY REFORMING OF Gülşen Doğu, Timur Doğu
METHANE
SEAF26
THE ROLE OF PRECIOUS METALS ON Deniz Kaya, Dheerendra Singh, Deniz Üner
ADSORPTION/DESORPTION KINETICS OF
OXYGEN OVER REDUCIBLE OXIDES
SEAF27
MODELING OF DATABASE CONSTRUCTED Elif Can, Ramazan Yıldırım,
FROM PUBLISHED ARTICLES FOR WATER
SPLITTING OVER PEROVSKITES
SEAF28
MORPHOLOGY OF PT-CU NANOPARTICLES Ezgi ERDEM, Rıza KIZILEL, Can ERKEY
BY USING GENETIC ALGORITHM AND
DENSITY FUNCTIONAL THEORY
Catalytic Conversion of renewable resources
TITLE
AUTHOR(S)
CRS1
TEMPERATURE EFFECT ON THE CARBON Dilsad Dolunay Eslek Koyuncu, Sena
DIOXIDE SORPTION CAPACITY OF NATURAL Yasyerli, Nail Yasyerli
MAGNESITE DERIVED SORBENT
CRS2
PREPARATION SUPPORTED PT AND RU Bahar Meryemoglu, Mehtap Kurtulus, Arif
CATALYASTS AND THEIR PERFORMANCES Hasanoglu, Sibel Irmak
IN AVPR PROCESS
CRS3
Investigation of Metal Loading Ratio Effect Nurgül ÖZBAY, Pınar BAŞ, Adife Şeyda
on Characteristics of Co/Al2O3 Catalysts YARGIÇ
and Utilization in Catalytic Pyrolysis
CRS4
AN EFFICIENT HETEROGENEOUS CR- Merve Esen, Esra Sezgin, Solmaz Akmaz,
ZEOLITE CATALYST FOR GLUCOSE Serkan Naci Koç, M. Ali Gürkaynak
TO
5-HYDROXYMETHYLFURFURAL
CONVERSION
CRS5
N-HETEROCYCLIC
CARBENE-BASED Deniz DEMİR ATLI, Şebnem E. SÖZERLİ
NICKEL(II) COMPLEXES IN KUMADA
COUPLING
CRS6
Sorption Enhanced Steam Reforming of Merve Sarıyer, Arzu Arslan, Naime Aslı
Ethanol Over Ni Impregnated SBA-15 Sezgi, Timur Doğu
Catalyst
25
CRS7
ESTERIFICATION OF GLYCEROL WITH Gamze AY, Giray MUTLU, Emre KILIÇ,
OLEIC ACID OVER Ti CONTAINING Hasan ÖRTÜN, Selahattin YILMAZ
SULFATED SBA-15 CATALYSTS
CRS8
Synthesis and Characterization of Nurgül ÖZBAY, Rahmiye Zerrin YARBAY
Perovskite Catalyst and Its Catalytic ŞAHİN
Activity in Pyrolysis
CRS9
EPOXIDATION OF METHYL OLEATE OVER Vahide Nuran Mutlu, Canan TAŞ, Selahattin
SO4/TiO2-SiO2 AND WO3-ZrO2 CATALYSTS YILMAZa
CRS10
THE EFFECT OF PEROXIDE ON Mehtap Kurtulus, Bahar Meryemoglu, Arif
BIOMASS HYDROLYSIS AND CATALYTIC Hasanoglu, Sibel Irmak
GASIFICATION OF HYDROLYSATES
Catalytic membranes and nanostructured catalysts
TITLE
AUTHOR(S)
MNC1
Palladium(0) Nanoparticles Supported Metin Celebi, Mehmet Yurderi, Ahmet
on Amine-Functionalized Silica for the Bulut, Murat Kaya, Mehmet Zahmakiran
Catalytic Hexavalent Chromium Reduction
MNC2
PALLADIUM NANOPARTICLES(Pd NPs) Burcu DARENDELİ, Fatma Ulusal, Bilgehan
AS EFFICIENT CATALYSTS FOR SUZUKI- GÜZEL
MIYAURA REACTION IN MILD CONDITIONS
MNC3
Investigation of Isobutane Dehydrogenation Saliha Çetinyokuş Kılıçarslan, Meltem
Doğan, Timur Doğu
in a Pd-membrane Reactor
MNC4
PREPARATION OF NOVEL VIC-DIOXIME- Özge Atış, Fatma Ulusal, Bilgehan Güzel
Pd(II) COMPLEX FOR SUZUKI-MIYAURA
REACTIONS
MNC5
POTENTIAL APPLICATIONS OF SOLID Ümit YAŞAR, Fatma ULUSAL, Bilgehan
SUPPORT
CATALYTIC
MEDICAL GÜZEL, Pınar Yılgör HURİ, Nurten DİKMEN
MOLECULAR
MNC6
AMMONIA SYNTHESIS REACTION ON Ru M.Y.Aslan, S. Akbayrak, S. Özkar, D. Üner
NANOPARTICLES
MNC7
ARTIFICIAL
HUMAN
BLOOD AND Ümit YAŞAR, Fatma ULUSAL, Bilgehan
ANTIOXIDANT
ENZYME
CATALYSIS: GÜZEL, Pınar Yılgör HURİ, Nurten DİKMEN
GLUTATHIONE PEROXIDASE, CATALASE
MNC8
Ruthenium Nanoparticles Stabilized Yaşar Karataş, Ahmet Bulut, Mehmet
Hidrotalcite Catalyst for the Methanolysis Yurderi, Mehmet Gülcan, Mehmet
of Ammonia-Borane under Mild Conditions Zahmakıran
MNC9
EFFECT OF CRYSTAL STRUCTURE ON Fatma Ulusal, Burcu Darendeli, Özge Atış,
THE CATALYTIC ACTIVITY FOR SUZUKI- Mustafa Kemal Yılmaz, Bilgehan Güzel
MIYAURA COUPLING REACTION
26
MNC10
Sulfonic Acid Functionalized MIL-101 Nurdan Caner, Ahmet Bulut, Mehmet
Metal Organic Framework Confined Yurderi, Mehmet Zahmakıran
Palladium(0) Nanoparticles Catalyst for the
Methanolysis of Ammonia-Borane under
Mild Conditions
MNC11
IMMOBILIZATION
OF
GLUTAMATE Yusuf Döğüş, Gülüzar Özbolat, Hasan
DEHYDROGENASE ONTO AMİNATED Ulusal, Nevin Yılmaz, Abdullah Tuli
CARBON NANOTUBE AND INVESTIGATION
OF CATALTIC ACTIVITY
MNC12
IMMOBILIZATION OF XANTHINE OXIDASE Yusuf Döğüş, Gülüzar Özbolat, Hasan
ONTO AMINATED CARBON NANOTUBE Ulusal, Nevin Yılmaz, Abdullah Tuli
AND INVESTIGATION OF CATALTIC ACTIVITY
AND STABILIZATION
MNC13
THE INVESTIGATION OF DIMETHYGLOXIME Gülüzar Özbolat, Hasan Ulusal ,Yusuf
LIGAND WHICH CAN BE USED FOR Döğüş, Abdullah Tuli
ACCUMULATION OF IRON IN THE BODY ON
GLUTATATHIONE PEROXIDASE ENZYME
MNC14
THE INVESTIGATION OF DIMETHYGLOXIME Gülüzar Özbolat, Hasan Ulusal ,Yusuf
LIGAND WHICH CAN BE USED FOR Döğüş, Abdullah Tuli
ACCUMULATION OF IRON IN THE BODY ON
XANTHINE OXIDASE ENZYME
MNC15
PREPARATION AND APPLICATION OF Derya Unlu, Aynur Hacıoglu, Nilufer
AlK(SO4)2.12H2O LOADED CHITOSAN/ Hilmioglu
POLYVINYLPYRROLIDONE
CATALYTIC
MEMBRANE
MNC16
PHOSPHOTUNGSTIC
ACID
LOADED Filiz Ugur Nigiz, Nilufer Durmaz Hilmioglu
CELLULOSE MEMBRANE PREPARATION
FOR CATALYTIC MEMBRANE REACTOR
MNC17
PALLADIUM(II)-SCHIFF BASE COMPLEX Ayşen Berna Tekin, Bilgehan Güzel
SUPPORTED ON MWCNT FOR USING
AS CATALYST IN THE SUZUKI-MIYAURA
REACTION
MNC18
Metal Organic Framework (MIL-101) Ilknur Efecan Ertas, Mehmet Gulcan,
Stabilized Ruthenium(0) Nanoparticles: Ahmet Bulut, Mehmet Yurderi, Mehmet
Highly Efficient Catalytic Material for the Zahmakiran
Selective Hydrogenation of Phenol to
Cyclohexanone
MNC19
Trimetallic PdAuNi Alloy Nanoparticles Mehmet Yurderi, Metin Çelebi, Ahmet
Supported on Amine Functionalized Bulut, Mehmet Zahmakıran
Reduced Graphene Oxide for the
Dehydrogenation of Formic Acid Under
Mild Conditions
27
Catalytic methods for air water pollution control
TITLE
AUTHOR(S)
AWPC1
Synthesis and insitu catalytic aplication of Sedat YAŞAR, Emine Özge KARACA, Nevin
GÜRBÜZ,İsmail ÖZDEMİR
7-BER-NHC ligands on Suzuki reaction
AWPC2
Improvement of Sulfur Regenaration Z. Aybegum Samast, Emrah Ozensoy
Ability of NSR Catalysts via Reducible
Mixed Oxide Promoters
AWPC3
Selective CO2 adsorption studies on NaOH B. M. Eropak, B. S. Çağlayan, A. E. Aksoylu
impregnated AC Adsorbents
AWPC4
Spectroscopic Investigation of NOx Merve Tohumeken, Zafer Say, Emrah
Storage and Reduction Pathways on Pt/ Ozensoy
K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts
AWPC5
Removing of Synthetic Dyes from Aqueous Ali Kara, A.Çiğdem Karaerkek
Solutions By Using Photocatalysis and
Adsorption Methods
28
POSTER PRESENTATIONS 29/04/2016
Electrochemical and photochemical catalysts
TITLE
AUTHOR(S)
EPC1
ANODIC BEHAVIOR OF CARBON SUPPORTED Alpay ŞAHİN, İrfan AR,
Ni-Co, Ni AND Co ELECTROCATALYST IN
DIRECT BOROHYDRIDE FUEL CELL
EPC2
THE POLYANILINE FILMS on ZnNi PLATED Nureddin Colak, A.Tuncay
Ibrahim Filazi
COPPER ELECTRODE
EPC3
BASED
ELECTROCATALYST Büşranur DUMAN, Berker FIÇICILAR
Mn3O4
SYNTHESIS FOR VANADIUM REDOX FLOW
BATTERIES
EPC4
Synthesis,
Characterization
and Kadir KARAKAŞ, Metin ÇELEBİ, Mehmet
Photocatalytic Performance of Ag\ZnO in ZAHMAKIRAN
the Photodegradation of Methylene Blue
under UV Irradiation
EPC5
SYNTHESIS
OF
CNT-TiO2-SiO2 Tuğçe Kırbaş, Gürkan Karakaş
NANOCOMPOSITE THIN FILMS: THE
EFFECT OF HEAT TREATMENT ON
PHOTOCATALYTIC ACTIVITY
EPC6
Determination of Reaction Kinetics for Bahadır K. KÖRBAHTİ, Selin ALACA
Electrochemical Oxidation of Tetracycline
Antibiotic using Boron-Doped Diamond
Anode
EPC7
THE
ELECTROCATALYTIC
BEHAVIOR A.Tuncay Ozyilmaz, Gul Ozyilmaz, İ.Hakkı
OF COPOLYMER FILMS ON ZnFeCo Karahan
DEPOSITED CARBON STEEL ELECTRODE
EPC8
ELECTROCATALYTIC
CONDUCTING A.Tuncay Ozyilmaz, Gul Ozyilmaz, İ.Hakkı
POLYMER FILMS ON Zn DEPOSITED Karahan
CARBON STEEL ELECTRODE
EPC9
COBALT-BASED
COORDINATION Emine Ülker, Aysun Tekin , Satya Vijaya
COMPOUNDS FOR ELECTROCATALYTIC Kumar Nune, Ferdi Karadaş
WATER OXIDATION
EPC10
DETERMINATION OF OPTIMUM Cu-CeO2 Vedat Sarıboğa, M.A. Faruk Öksüzömer
ANODE COMPOSITION FOR DIRECT
METHANE SOLID OXIDE FUEL CELL
EPC11
Characterization of PAni-Fe Electrocatalyst Göknur Dönmez, Merve Deniz, Hüseyin
Loaded on Multi-walled Carbon Nanotube Deligöz,
Support
Ozyilmaz,
EPC12
29
Benzene Oxidation as an Alternative M.M. Oymak, T. Tabari D. Uner
Method for Assessing Photocatalytic
Activity
Environmentally friendly catalytic processes
TITLE
AUTHOR(S)
EFCP1
Pd-PEPPSI-Type N-Heterocyclic Carbene Murat Kaloğlu, İsmail Özdemir, Henri
Complexes: Synthesis, Characterization Doucet, Christian Bruneau
and Catalytic Activity in The Direct
Arylation Reactions
EFCP2
SYNTHESIS STUDIES OF THE PROMISING Emine EKİNCİ
CATALIST; MIL-101
EFCP3
Synthesis of Chiral Catalysts and Their Aysen DEMİR, Burcu DARENDELİ, Bilgehan
GÜZEL
Catalytic Activities in ScCO2
EFCP4
GREEN
DEHYDROGENATION
OF BERİVAN BUKAN, Sibel DUMAN
DIMETHYLAMINE-BORANE CATALYZED BY
PVP, Al2O3 AND PS-co-MA STABILIZED Ru
NPs
EFCP5
Catalytic applications and synthesis Nazan Kaloğlu, İsmail Özdemir, Henri
of Pd-PEPPSI N- Heterocyclic Carbene Doucet, Christian Bruneau
Complexes
EFCP6
Synthesis of poly(cyclooctene) derivatives Gülşah ÇALIŞGAN, Bengi Özgün ÖZTÜRK,
bearing imidazole end group by ROMP Solmaz KARABULUT ŞEHİTOĞLU
Reactions
EFCP7
Direct Arylation
Complexes
EFCP8
Magnetic Nanoparticle Supported Latent Bengi Özgün ÖZTÜRK, Solmaz KARABULUT
Ruthenium Metathesis Catalysts for Olefin ŞEHİTOĞLU
Metathesis Reactions
EFCP9
Modification of Functional Polyesters by Didem OKUR, Bengi Özgün ÖZTÜRK,
Metathesis Reactions in the Presence of Solmaz KARABULUT ŞEHİTOĞLU
Hoveyda-Grubbs Type Catalysts
EFCP10
Synthesis
of
Fe3O4@SiO2@ Serhan Uruş
RN(CH2PPh2)2PdCl2 Type Nanocomposite
Catalysts for Vitamin K3 Synthesis
EFCP11
Modification of Poly(norbornenediester) Elif Ak, Elif Yakut, Bengi Özgün ÖZTÜRK,
Derivatives with Primary and Secondary Solmaz KARABULUT ŞEHİTOĞLU
Amine Groups
EFCP12
Reusability of nano-12-tungstophosporic Elif AKBAY, Gülberk DEMİR
acid cesium salt in alkylation of benzene
with dec-1-ene reaction
with
Palladium-NHC Emine Özge KARACA, Nevin GÜRBÜZ,
Sedat YAŞAR, İsmail ÖZDEMİR
30
EFCP13
Alumina Supported Mn-Ce Sorbents Melike Kucuker, Sena Yasyerli, A. Derya
for High Temperature Desulfurization of Deniz Kaynar
Hydrogen Rich Gas Mixtures
EFCP14
Catalytic Wet Peroxide Oxidation of Fatma TOMUL
Bisphenol A in Water
EFCP15
Graphene
Supported Serhan Uruş, Mahmut Çaylar, İbrahim
Aminomethylphosphine-Pd(II) and Pt(II) Karteri
Complexes: Highly Efficient Catalysts on
Vitamin K3 Synthesis
EFCP16
N-Alkylation Reaction with Functionalized Nevin GÜRBÜZ, Emine Özge KARACA,
Sedat YAŞAR, İsmail ÖZDEMİR
Ionic Liquids
EFCP17
The Coupling Reaction With Aryl Grignard İsmail Özdemir, Serpil Demir Düşünceli,
Reagents in the Presence of Iron/NHC Nevin Gürbüz
Catalyst
EFCP18
Palladium-NHC Complex Catalyzed Cross Serpil Demir Düşünceli, Rukiye Zengin
Yaman, İsmail Özdemir
Coupling Reactions
EFPC19
PHOTOCATALYTIC WATER SPLITTING OVER Ramazan Yıldırım, Dilara Saadetnejad
Au/SrTiO3 CATALYST
EFCP20
IN SITU GENERATION COPPER(0) Sibel DUMAN
NPs AND CONCOMITANT GREEN
DEHYDROGENATION OF DIMETHYLAMINEBORANE
EFCP21
Synthesis of Palladium(II) Schiff Base Sinan SEVEN, Figen KOÇAK, Bilgehan
Complex And it’s Catalytic Activities C-C GÜZEL
Coupling Reactions
Hydrogenation catalysts
TITLE
AUTHOR(S)
HYD1
HYDROBENZOIN TYPE LIGANDS FOR Seda KILIÇARSLAN, Halil Zeki GÖK, İlker
Ümit KARAYİĞİT, Yaşar GÖK
ASYMMETRIC CATALYSIS
HYD2
THE
SYNTHESIS
OF
MAGNETIC Eylül Büşra Hereytani, Fatma Ulusal,
NANOPARTICLES
SUPPORTED Bilgehan Güzel
AZOMETHINE-OXIME-PD COMPLEX AND
ITS CATALYTIC ACTIVITY
HYD3
N - S u b s t i t u t e d b e n z i m i d a z o l e - Kenan Buldurun, Nevin Gürbüz, İsmail
Ruthenium(II) Complexes
and Their Özdemir
Catalytic Activity
HYD4
Determination of Radiation Absorption A.Çiğdem Karaerkek, Faruk Demir, Ali Kara
Properties
of
Gamma
Irradiated
Polyoxovanadate Based Catalysts
31
HYD5
EFFECTS OF THE PREPARATION METHOD Filiz BALIKÇI DEREKAYA
AND CALCINATION TEMPERATURE ON THE
CHARACTERISTIC PROPERTIES OF NiOFe2O3-SiO2 CATALYSTS
HYD6
MODULAR LIGANDS ALLOWING TUNABLE Yaşar GÖK, Seda KILIÇARSLAN, Halil Zeki
STERIC AND ELECTRONIC EFFECTS FOR GÖK, İlker Ümit KARAYİĞİT
TRANSITION METAL CATALYSIS
New catalytic approaches to oil refining and petrochemistry
TITLE
AUTHOR(S)
ORP1
Synthesis of Tungstophosphoric Acid M. İlker Şener, Naime Aslı Sezgi, Timur
Incorporated
Mesoporous
Alumina Doğu, Gülşen Doğu, Nuray Oktar
Catalysts for Methanol Dehydration in
DME Synthesis
ORP2
Production of 2,6-Dimethylnaphthalene Eda Karayılan, Aysun Özen, Fatih Güleç, Ali
with Methylation of Naphthalene over Au/ Karaduman
Mordenite Zeolite Catalysts
Oxidation catalysts
TITLE
AUTHOR(S)
OXC2
CHARACTERIZATION
OF
Ni/ZrTiO4 Burcu Aygün, Hasan Özdemir, M.A. Faruk
CATALYST FOR THE PARTIAL OXIDATION of Öksüzömer, Serkan Naci Koç
METHANE
OXC3
Characterization
and
Catalytic Mahmut Yildiz, Reinhard Schomaecker
Performance of MnxOy-Na2WO4/SiO2 for the
Oxidative Coupling of Methane
OXC4
The Effect of Metal Adding Sequence Filiz AKTI, Suna BALCI, Timur DOĞU
and Synthesis Media on the Properties of
SnSBA-15 Catalysts at Low Metal Ratio
OXC5
Effect of Ti-Ce Content on the Catalytic H.Mehmet Tasdemir, Yavuz Yagizatli, Sena
Activity of Alumina Supported Catalysts in Yasyerli, Nail Yasyerli, Gulsen Dogu
Selective Oxidation of H2S
OXC6
INVESTIGATION AND CHARACTERIZATION Burcu Aygün, Hasan Özdemir, M.A. Faruk
OF Ni/MgO CATALYST PREPARED BY Öksüzömer, M. Ali Gürkaynak
ELECTROSPINNIG TECHNIQUE FOR THE
PARTIAL OXIDATION AND DRY REFORMING
OF METHANE
OXC7
THE CATALYTIC ACTIVITY OF AZO Mesut İKİZ, Esin İSPİR
CONTAINING SCHIFF BASE COMPLEXES
OXC8
TRANSITION METAL COMPLEXES OF Cahit Demetgül, Neslihan Beyazıt
NOVEL CHROMONE SCHIFF BASES:
SYNTHESIS, CHARACTERIZATION AND
CATECHOLASE-LIKE ACTIVITY
32
OXC9
Hydrothermal
Synthesis
and Burak AY, Emel YILDIZ
Characterization
of
Heterogeneous
Catalysts for the Oxidation of the Thymol
To Thymoquinone
OXC10
SUITABLE CATALYST OBTAINING FOR Mehmet TÜMER,
ALKANE OXIDATION AND ALKENE Ferhan TÜMER
EPOXIDATION REACTIONS
Muhammet
KÖSE,
OXC11
POLYMER SOLID SUPPORT CATALYSTS Mehmet TÜMER,
Ferhan TÜMER
FOR ALKANE OXIDATION
Muhammet
KÖSE,
OXC12
CATALYST
DESIGN
EPOXIDATION
ALKENE Mehmet TÜMER,
Ferhan TÜMER
Muhammet
KÖSE,
OXC13
New Ferrocene Based Schiff Bases Metal Gökhan CEYHAN
Complexes: Synthesis and Investigation of
Catalytic Activities
OXC14
Oxidation of alkanes with hydrogen Gökhan CEYHAN
peroxide catalyzed by ferrocene
OXC15
Transition Metal Complexes of Ligand in a Gökhan Ceyhan, Savaş Purtaş
Liquid Crystal Properties: Investigation of
the Catalytic Activity
OXC16
Novel Gallic Esters: Its Synthesis, Structural Gökhan Ceyhan, Savaş Purtaş
Characterization,
Photoluminescence,
Electrochemical Properties And Alkene
Epoxidation
OXC17
Catalytic activity of Schiff Base Mn(III)/ Büşra GENÇOĞLU, Pınar Şen, Salih Zeki
Yıldız
Co(III) complexes on bleach catalyst
OXC18
Catalytic Oxidation of Nitrogen Containing Alper SEVİNÇ, Gürkan KARAKAŞ, İ. Bülent
ATAMER
Compounds for Nitrogen Determination
OXC19
Catalytic Properties of ONO Type Gökhan Ceyhan, Münire Sarıgül,
Muhammet Köse, and Mukerrem Kurtoglu
Salicylaldimine Copper(II) Complexes
OXC20
Copper Complexes with Bidentate NO Gökhan Ceyhan, Sevgi Kahraman,
Ligands as Novel Catalysts for the Muhammet Köse, and Mukerrem Kurtoglu
Homogeneous Partial Oxidation of Alkanes
OXC21
The comparison of catalytic activity of non- Pınar ŞEN, Salih Zeki YILDIZ
ionic and ionic Mn(III)/Co(II) Phthalocyanine
complexes on bleach systems
OXC22
THE CATALYTIC ACTIVITY OF NOVEL, AZO- Ayşe İNAN, Mesut İKİZ, Esin İSPİR
CONTAINING SCHIFF BASES AND THEIR
METAL COMPLEXES
FOR
33
OXC23
Investigation of Oxidation Reaction Mustafa Karatok, Evgeny Vovk, Asad A.
Pathways of Oxygenates on Au(111) Single Shah, Emrah Ozensoy
Crystal Depending on the Behaviour of
Oxygen
OXC24
Effective Catalysts Derived from Carbazole Selma Bal
for Alkene oxidation
OXC25
Schiff base transition metal complexes Ozge Eren, Harun Muslu, Gökhan Ceyhan,
with
ceftazidime: Synthesis
and Mehmet Tumer and Aysegul Golcu
Investigation of Alkane Oxidation
OXC26
Drug metal complexes: Synthesis and Ozge Eren, Derya Kılıcaslan, Gökhan
Ceyhan, Mehmet Tumer and Aysegul Golcu
Investigation of Alkane Oxidation
Zeolites and mesoporous catalytic materials
TITLE
AUTHOR(S)
ZMC1
Synthesis and Characterization of MCM- Nurbanu Çakıryılmaz, H. Arbağ, N. Oktar, G.
41 Supported Ni Catalysts for Acetic Acid Doğu, T. Doğu
Steam Reforming
ZMC2
COMPARISON OF FRESH FCC CATALYSTS, Deniz Onay Atmaca, Melek Bardakcı
E-CAT SAMPLES and FCC ADDITIVES FOR Türkmen, Burcu Yüzüak, Ayşegül Bayat,
Ersen Ertaş
COMPREHENSION OF THE PROCESS
ZMC3
Hydrogen Adsorption on M2+-LTL Zeolite Mehmet Ferdi FELLAH
Clusters (M = Be, Mg and Ca): A Density
Functional Theory Study
ZMC4
Investigation of Surface Acidity of Metal/ Hülya MADENCİOĞLU and Ali KARADUMAN
Bimetal Modified Zeolite Catalysts using
Pyridine Probe Molecule by FT-IR
ZMC5
Synthesis and Characterization of CMK-3 Gülce ÇAKMAN , Nahide NARİN, Feza
GEYİKÇİ
and Activated Carbon Based Catalysts
ZMC6
IMPACT
OF
HYDROCRACKING Melek Bardakcı Türkmen, Burcu Yüzüak,
CATALYST CHARACTERISTICS ON THE Ayşegül Bayat, Deniz Onay Atmaca, Ersen
PERFORMANCE OF HYDROCRACKING UNIT Ertaş
ZMC7
AMMONIA DECOMPOSITION REACTION Yeliz DURAK-ÇETİN, Şerife SARIOĞLAN,
OVER ZEOLITE Y SUPPORTED IRON Alper SARIOĞLAN, Hasancan OKUTAN
CATALYSTS: EFFECT OF DEALUMINATION
ZMC8
Palladium (II) Schiff Base Complexes: Asım Eğitmen, Bilgehan Güzel
Precursor for the Deposition onto the
mesoporous SBA-15 in scCO2 Media
ZMC9
Synthesis and Characterization of SBA15 Taner Tuncer, Gizem Akbıyık, Tuğba
Mesoporous Materials Functionalized with Candaş, Alime Çıtak
Boron Metal
34
ZMC10
Determination of ΔH°, ΔS° and ΔG° Sercan Koç, Tuğçe Güner, Alime Çıtak
values of B-SBA15 Mesoporous Materials
Using Inverse Gas Chromatography
Technique
ZMC11
Single Step Synthesis of HPA loaded Al- Suna BALCI, M.Candan KARAEYVAZ, Gulce
ACIL, Funda TURGUT BASOGLU
PILCs
ZMC12
Zeolite Catalysis for Bio-oil Upgrading via Ayşenur Yeşilyurt, Ayşe Gül Türe, H. Levent
Hoşgün
Esterification
Lectures
(Abstracts)
35
36
Support Effect in Oxide Catalysis: C-H Bond Activation on
Vanadia/Ceria Compared to Vanadia/Silica
Joachim Sauer
Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany
Density functional theory is used for periodic models of monomeric vanadia species
deposited on the CeO2(111) surface to study dissociative adsorption of methanol and
its subsequent dehydrogenation to formaldehyde.1 Dissociative adsorption of methanol
at different sites on VO2·CeO2(111) is highly exothermic with adsorption energies
of 1.8 to 1.9 eV. Two relevant pathways for desorption of formaldehyde are found
with intrinsic barriers for the redox step of 1.0 and 1.4 eV. The calculated desorption
temperatures (370 and 495 K) explain the peaks observed in temperature-programmed
desorption experiments. Different sites of the supported catalyst system are involved
in the two pathways: (i) methanol can chemisorb on the CeO2 surface filling a socalled pseudovacancy and the H atom is transferred to an V–O–Ce interphase bond
or (ii) CH3OH may chemisorb at the V–O–Ce interphase bond and forms a V–OCH3
species from which H is transferred to the ceria surface, providing evidence for true
cooperativity.
Compared to the vanadia-silica system,2 the vanadia –ceria system is a more active
catalyst both because methanol binds more strongly on the surface and the intrinsic
barriers for the hydrogen transfer step are lower. The reason is the direct participation
of ceria in the redox process. On non-reducible supports like silica vanadia is reduced,
whereas ceria as support stabilizes vanadium in its highest oxidation state.
References
1. Kropp, T.; Paier, J.; Sauer, J., Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/
Ceria. J. Am. Chem. Soc. 2014, 136, 14616-14625.
2. Döbler, J.; Pritzsche, M.; Sauer, J., Oxidation of Methanol to Formaldehyde on Supported
Vanadium Oxide Catalysts Compared to Gas Phase Molecules. J. Am. Chem. Soc. 2005, 127,
10861-10868.
37
Catalysis for bio-olefins production: from research to industrial
application
Fabrizio Cavani
Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4,
40136 Bologna, Italy
In the context of a more sustainable chemical industry, the invention of new (or
reconsidered) processes for the synthesis of C2-C4 olefins from renewables is of crucial
importance, since these molecules are fundamental building blocks for the production
of polymers and intermediates. For example, butadiene is an important monomer
for the production of synthetic rubber (principally for making tires and automobiles
components). In this lecture the production of C4 olefins from renewable sources is
discussed, highlighting the technologies involved and the best performing catalysts.
Among the viable options, particular focus is given to the more environmentally benign
and sustainable routes, that are the syntheses involving the least possible number of
steps and relatively mild reaction conditions. One important example is the process
for the production of butadiene from bio-ethanol. This technology was implemented
at an industrial level in several countries, such as Russia, USA, Poland and Italy, during
the years 1930-1950, because of the urgent need to develop an autarchic production of
strategic chemicals for the 2nd World War. After the end of the war, the interest for the
use of ethanol for chemicals production declined rapidly, because of the advent of the
economically more convenient production from oil. Nowadays, because of both the
advent of bio-ethanol production from lignocellulosic biomasses, and the scarcity of
butadiene due to the shift of several cracker units from naphtha to ethane feedstock,
several chemical companies have decided to investigate again old technologies for
the on-purpose production of butadiene. We have investigated the mechanism of
the transformation of ethanol into butadiene on bifunctional acid-base catalysts, by
combining reactivity experiments, DFT calculations and in-situ DRIFT spectroscopy
measurements [1,2].
References
[1] A. Chieregato, J. Velasquez Ochoa, C. Bandinelli, G. Fornasari, F. Cavani, M. Mella,
ChemSusChem 8 (2015) 377.
[2] J. Velasquez Ochoa, C. Bandinelli, O. Vozniuk, A. Chieregato, A. Malmusi, C. Recchi, Fabrizio
Cavani, Green Chem. 18 (2016) 1653.
38
Synthesis-Structure-Performance Relationships for
Heterogeneous Catalysts
Krijn P. de Jong
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science Utrecht University,
The Netherlands
Supported metal catalysts are widely used for the production of transportation
fuels and chemicals as well as in environmental catalysis. The metal nanoparticles are
typically 1-10 nm in size and often suffer from growth during catalysis. First results on
the relationship between synthesis, structure and performance for the conversion of
synthesis gas (a mixture of CO and H2) will be addressed for supported Co, Cu, Ni and
Fe catalysts. Second, control over the nanoscale distribution of Pt in alumina-zeolite
composite catalysts will be related to the performance for hydrocracking of alkanes.
39
Hydrogenation and Hydrogenolysis Reactions Involved
in Treatment of Water Contaminated with Chlorinated
Hydrocarbons
Umit. S. Ozkan
The Ohio State University, Columbus, Ohio – USA
Contamination of ground water by chlorinated hydrocarbons such as carbon
tetrachloride (CTC), tetrachloroethene (PCE), trichloroethene (TCE) and
1,1,1-trichloroethane (TCA) is a growing environmental concern. The current methods
to treat water contaminated with chlorinated hydrocarbons are expensive, due to
high energy requirements and media replacement costs, and serve only to transfer
contaminants from one phase to another, such as from water to air or from water
to landfills. While elimination of these contaminants by catalytic hydrogenation and
hydrodehalogenation offers a treatment strategy, there are challenges, such as the need
to run these reactions at low temperatures as well as the very low concentrations of the
contaminants in water. An equally important challenge is the poisoning of the catalysts
by sulfides and nitrates.
Catalytic systems developed by using swellable organosilicates as catalyst scaffold
have the potential to meet the challenges involved in catalytic hydrogenation and
hydrogenolysis of water contaminants. Swellable organically modified silicates (SOMS)
offer unique characteristics such as high affinity for absorbing organics while repelling
water due to their hydrophobicity. The swelling capability of these materials allows
active metals (precious metals, transition metals) dissolved in organic solvents to be
deposited inside the pores, thus forming active sites “protected” in a hydrophobic
matrix. This property also allows concentration of organic contaminants inside the
pores, near the active sites, hence accelerating the kinetics. The presentation will
discuss the use of swellable organosilica materials as a catalyst scaffold for precious and
transition metals and examine their use in water treatment strategies. Characterization
results from different techniques such as NMR, laser Raman spectroscopy, TEM, XPS,
and infrared spectroscopy will also be presented.
40
Energy Intensified Reactor Design with Radio Frequency Heating
Volkan Değirmenci
University of Warwick, School of Engineering
In a conventional heating system in chemical reactors the heat is generated externally
and transferred through the reaction medium. In our novel reactor design the magnetic
catalyst bodies generate heat by the use of an external magnetic field through radio
frequency (RF) heating. Local heat generation at the catalyst body prevents heat
transfer limitations and the formation of overheated hot zones in the reactor. The
precise control of temperature provides a more selective and thus a greener synthesis
platform for fine chemicals. Furthermore, cascade reactions are performed in single
pass continuous flow reactor with dual temperature and catalyst zones, which is a fine
example of process intensification.
41
STRUCTURE-PERFORMANCE RELATIONSHIPS IN SUPPORTED
METAL CATALYSTS WITH IONIC LIQUID LAYER
Alper Uzun
Koç University, Department of Chemical and Biological Engineering, Sariyer, 34450, Istanbul
Tuning the electronic environment on metal sites can help to control the selectivity
performance of supported metal catalysts. For this purpose, coating supported
metal catalysts with an ionic liquid (IL) layer offers tremendous potential. The
tunable physiochemical properties of ILs play a role in controlling selectivity by not
only determining the electronic environment of active sites (ligand effect), but also
in controlling the active concentrations of reactants and intermediates (filter effect).
In this talk, recent results on the structure-performance relationships in supported
metal catalysts with IL layer will be presented. The first part of the talk will illustrate the
performance improvements of a commercial supported nickel catalyst for an industrially
relevant reaction, partial hydrogenation of 1,3-butadiene. Data show that upon coating
the nickel catalyst with ILs, the selectivity to butenes increases from less than 1 % to
values exceeding 96 % irrespective of conversion. XPS results indicate that this increase
in selectivity is associated with electron donation from ILs to nickel sites. Density
functional theory calculations confirm that the ILs strongly influence the electronic
environment over the nickel sites. This change in electronic environment results in a
strong decrease in the binding energies of butenes over the active sites. Thus, the results
confirm that butene molecules formed in the first step of 1,3-butadiene hydrogenation
cannot stay over the active sites, and they are replaced 1,3-butadiene molecules which
can bond more strongly, as a result of electron donation from ILs to the metal sites. In
the second part of the talk, the effects of ILs on metal sites will be further illustrated
at the atomic level. Highly uniform and site-isolated iridium complexes supported on
various metal oxides were coated with almost 40 different ILs. Infrared spectra of these
samples illustrate that IL structure can be adjusted to tune the electronic environment
on the metal sites. These results offer opportunities for the rational design of supported
metal catalysts with IL layer for superior selectivity towards desired products for various
reactions.
This study is supported by TUBITAK under 3501 Program (113M552). A.U. acknowledges
the BAGEP Award of the Science Academy, Turkey.
42
Oral Presentations
(Abstracts)
43
Catalytic Role of Pyrite on Hydrodesulfurization of Lignite and
Asphaltite
Veysi Halvacia, Arzu Kancab, Deniz Unera
a
Chemical Engineering Department, Middle East Technical University, 06800 Ankara, TURKEY
b
Chemical Engineering Department, Ataturk University, 25240 Erzurum, TURKEY
Pyrite, FeS2, naturally present in solid fuels can act as catalysts during hydrogenation
processes. In general, metal sulfide catalysts are used as hydrogenation and
hydrodesulfurization processes of petroleum fractions. The defects in crystal lattice
were considered as the responsible parts of catalytic activity. Therefore, the presence of
metal sulfide active sites in the structure increases the process efficiency. Since pyrite is
a metal sulfide present in the coal structure, Guin et al. reported a higher reaction rate
in the presence of pyrite during hydrogenation process [1].
In this study, catalytic effect of pyrite has been investigated by hydrogenation of a
high sulfur Turkish lignite and asphaltite at atmospheric pressure. The first results of
hydrogenation experiments for Tuncbilek lignite with high pyrite content (2.6% in weight)
revealed that H2 reduction decreases the sulfur contents considerably. Additionally, the
amount of residual carbon decreased as observed from the decrease in CO2 formation
rate of hydrogenation residue during TPO. These effects are interpreted for the catalytic
effect of pyrite [2]. Hydrodesulfurization of Şırnak asphaltite with 1.59% pyrite, is carried
out under 100 sccm flow of 10% H2 and balance N2. Gas and liquid product analysis
indicated that hydrogenation of asphaltite results in a significant decrease in total sulfur
while producing nearly 20% liquid fuel, which contains organics from C6 to C26.
Acknowledgements
The authors kindly acknowledge Atalay Calisan for his assistance during experiments and METU
PAL for detailed hydrocarbon analysis.
Reference
[1] J.A. Guin, A.R. Tarrer, J.W. Prather, D.R. Johnson, J.M. Lee, Effects of Coal Minerals on
Hydrogenation, Desulfurization, and Solvent-Extraction of Coal, Industrial & Engineering
Chemistry Process Design and Development, 17 (1978) 118-126.
[2] A. Kanca, D. Matthew, J.A. Reimer, D. Uner, Following The Structure and Reactivity of
Tuncbilek Lignite During Pyrolysis and Hydrogenation, Fuel Processing Technology, Submitted
for publication. (2016).
44
REDUCED GRAPHENE OXIDE (RGO) SUPPORTED Pt
NANOPARTICLES: EFFECT OF DIFFERENT REDUCING AGENTS ON
RGO
Elif DAŞa, Ayşenur ÖZTÜRKb, Ayşe BAYRAKÇEKEN YURTCANa,b
a
Department of Nanoscience and Nanoengineering, Atatürk University, 25240, Erzurum
b
Department of Chemical Engineering, Atatürk University, 25240, Erzurum
Proton exchange membrane fuel cell (PEMFC) is a potential power source with high
efficiency and an attractive solution to global energy demand. However, one of the
most challenging problems that needs to be overcome is development of cost-effective
and durable electrocatalysts [1]. Carbon supported platinum (Pt/C) is a well accepted
catalyst on PEMFC and shows high electrochemical performance, but the corrosion of
carbon leads to the detachment of platinum nanoparticles from the support materials
and the aggregation of these particles causes the decrease of active surface area.
Recently, various carbon support materials with different nanostructures have been
used as the electrocatalyst support in PEMFCs.
Graphene, a monolayer of carbon atom in a crystal lattice, has received great attention
as a support material for PEMFC applications due to its basal plane structure with high
surface area and high conductivity.
In this study, graphene oxide (GO) was synthesized from natural graphite powder by the
method of Hummers and Offeman [2]. GO can be readily reduced by different reduction
processes and using different reducing agents. In this study, two different reducing
agents (hydrazine [3] and DMF [4]) were used. Pt nanoparticles were decorated on
reduced GO by using microwave irradiation technique. The properties were analyzed
by SEM, EDS, BET, TGA, FTIR, TEM and cyclic voltammetry (CV) techniques.
References
[1] F. Memioğlu, A. Bayrakçeken, T. Öznülüer, M. Ak, International Journal of Hydrogen Energy, 37
(2012) 16673-16679 .
[2] W.S. Hummers, R.E. Offeman J Am Chem Soc, 1958;80:1339-40
[3] Ö. Metin, E. Kayhan, S. Özkar, J.J. Schneider, International Journal of Hydrogen Energy, 37
(2012) 8161-8169.
[4] Ö. Metin, Ş. Aydoğan, K. Meral, Journal of Alloys and Compounds, 585 (2014) 681-688.
45
Catalytic Tar Removal on Nickel-loaded Perovskites
Basar Caglara, Taymaz Tabaria, Deniz Ünera,
a
Middle East Technical University, Chemical Engineering Department, 06531, Ankara, Turkey
Dry reforming of tar compounds has been studied on Ni loaded perovskites to gain
insight into conversion of tar compounds (produced by biomass gasification) into
synthesis gas. Nickel is a highly active hydrocarbon decomposition and water-gas shift
(WGS) catalyst suffering from coke deposition and sintering. Perovskite materials (e.g.
LaCoO3 and LaFeO3) are used to compensate the problems related to stability of nickel
catalyst by sintering and coke formation. Perovskites exhibit high thermal stability, high
oxygen storage/release capacity and high tar removal activity [1-3]. For this study, we
choose benzene as a model compound for tars. We have investigated dry reforming of
benzene on Ni/LaCoO3 at various Ni loadings, CO2 to benzene ratios and temperatures.
The conventional Ni/Al2O3 catalyst was also used as a reference material to determine
the relative activity of Ni/LaCoO3. Several techniques were used to characterize catalyst
materials: XRD to determine crystal structure, BET to determine surface area, pore
structure and volume of catalysts, Temperature Programmed Reduction (TPR) to
determine the reducibility of materials, XPS to detect the oxidation state and chemical
composition of the catalyst surface, TGA to determine the amount of carbon deposited
after reaction. We found that the reducibility of Ni/LaCoO3 catalyst is 4 times higher
than that of Ni/Al2O3 catalyst and the surface concentration of nickel is 4 times more
on Ni/LaCoO3 catalyst than that on Ni/Al2O3 catalyst. Due to its high surface nickel
concentration and reducibility, Ni/LaCoO3 catalyst shows two times higher benzene
conversion and H2 yield and less carbon formation than than the conventional Ni/Al2O3
catalyst.
References
[1] J. Suntivich, K.J. May, H.A. Gasteiger, J.B. Goodenough, Y. Shao-Horn, Science, 334 (2011)
1383-1385.
[2] R.J.H. Voorhoeve, D.W. Johnson, J.P. Remeika, P.K. Gallagher, Science 195 (1977) 827-833.
[3] P. Ammendola, L. Lisi, B. Piriou, G. Ruoppolo, Chemical Engineering Journal, 154 (2009) 361368.
46
Ultrasound assisted biodiesel production in presence of
dolomite catalyst
İbrahim Korkuta, Mahmut Bayramoğlua
a
Gebze Technical University, Chemical Eng. Department, 41400 Kocaeli, Turkey
Ultrasound (US) assisted transesterification of canola oil in presence of dolomite
catalyst. An US generator (200 W, 20 kHz) equipped with an horn type probe (19 mm)
as shown in Figure 1, was used to study the effect of catalyst amount (3-7 % wt. of oil),
methanol/oil molar ratio(4/1-15/1), ultrasound power (30-50 W), temperature (25 60° C) and time (60-120 min.) on US assisted biodiesel synthesis. As seen in Figure 2,
biodiesel yield reached over 97.4% for dolomite at the end of 90 min. According to the
results, US improved the transesterification reaction by reducing necessary time for
high biodiesel yield, using dolomite as heterogeneous catalyst.
Figure 1. Scheme of experimental setup
Figure 2. Effect of ultrasound irradiation time on the biodiesel yield (Transesterification conditions;
catalyst amount: 5% wt. of oil, methanol/oil molar ratio: 9/1, US power: 45 W, temperature: 60 °C)
47
Ruthenium(0) nanoparticles supported on xonotlite nanowire: a
long-lived catalyst for hydrolysis of ammonia-borane
Serdar Akbayrak, Saim Özkar
Department of Chemistry, Middle East Technical University, 06800 Ankara.
Ruthenium(0) nanoparticles supported on xonotlite nanowire (Ru(0)@X-NW) were
prepared by the ion exchange of Ru3+ ions with Ca2+ ions in the lattice of xonotlite
nanowire followed by their reduction with sodium borohydride in aqueous solution
at room temperature. Ru(0)@X-NW were characterized by a combination of advanced
analytical techniques. The results show that (i) highly dispersed ruthenium(0)
nanoparticles of 4.4 ± 0.4 nm size were formed on the surface of xonotlite nanowire, (ii)
Ru(0)@X-NW show high catalytic activity in hydrogen generation from the hydrolytic
dehydrogenation of ammonia borane with a turnover frequency value up to 135 min−1
at 25.0 ± 0.1 ºC. (iii) They provide unprecedented catalytic life time (TTO = 134,100)
for hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 ºC (Fig.1).
(iv) The results of a kinetic study on the hydrogen generation from the hydrolysis of
ammonia borane were also reported including the activation energy of 77 ± 2 kJ mol−1
for this reaction [1].
Figure 1. The variation in turnover number (TON) and turnover frequency (TOF) during the catalytic
lifetime experiment performed at 25.0 ± 0.1 °C.
References
[1] Serdar Akbayrak, Saim Özkar Dalton Trans., 2014, 43,1797.
48
Synthesis of STA/SBA-15 Catalysts for Ethyl Acetate Production
and Characterizations of Catalysts
Veli SIMSEKª, Kirali MURTEZAOGLUb
a
Bilecik Seyh Edebali University, Chemical and Process Engineering Department, 11100,
Gulumbe Campus, Bilecik.
b
.Gazi Universty, Chemical Engineering Department,06570, Maltepe Ankara.
Silicate structured mesoporous materials with larger surface areas, narrow pore size
distributions and high thermal stability are a good candidate for some application fields
and as support materials in the catalytic synthesis[1,2]. Although application of SBA15 as catalyst is unlikely due to it’s weak Lewis acidity and absence of Bronsted acid
sites, Bronsted acidity should be enhanced by impregnation and other methods[3].
For instance, the hydrothermal method has also been used for STA/SBA-15 catalysts
by Simsek et al[2,4]. Ethyl esters have long been attracted alternatives to biodisel
additives[5].
In the present study, STA was loaded by dry impregnation method after TEOS on SBA-15
support material. SBA-15 and STA (Silicotungstic acid) were used to support and active
material respectively. The loading amount of silicotungstic acid were determined as 1.25,
2.5, 5% (W/Si; w/w ratio). Actually this loading ratios are very low for the impregnation
method. But catalysts were succesfully synthesized by appyling impregnation method.
Ethanol/acetic acid molar ratio, temperature and catalyst amount were determined
as 1/1, 343 K and 0.4g respectively. The catalytic activities of STA/SBA-15 (2.5 and 5%)
catalysts were investigated in ethyl acetate reaction. The results showed that the
activity of catalysts increased with increasing active material(STA) in the catalyst. The
physical properties of the catalysts were determined with XRD, DRIFT, BET, SEM/EDX
and MAPPING analysis methods. The low angle XRD results of the catalysts revealed
characteristic peaks (100),(110) and (200) reflections. In order to determine Lewis and
Bronsted sites of the catalysts were used to pyridine and then analyzed FT-IR. The
results indicated that the catalysts had Lewis and Bronsted sites.
References
[1] Obalı, Z. Doğu, T. Chem. Eng. J. (2008) 138:548-555.
[2] Şimşek, V. Değirmenci L. Mürtezaoğlu K., Turk J. Chem.(2015) 39:683-696
[3] Ghiaci, M. Aghabarari, B. Chinese Journal of Catalysts (2010) 31: 759-764
[4] Şimşek, V. Değirmenci L. Mürtezaoğlu K., Reac Kinet Mech Cat.(2015) in press.
[5] Merchant, S. Q. Almohammad, K. A. Bassam, A. A. M. Ali, S. H. Fuel (2013) 111: 140-147
49
INVESTIGATION OF CATALYST, REACTION CONDITIONS AND
PROCESS DESIGN FOR HYDROGEN PRODUCTION FROM STEAM
REFORMING OF GLYCEROL
Öykü Parlar, M. Efgan Kibar, A. Nilgün Akın, Meltem Karaman
Kocaeli University, Chemical Engineering Department, 41380, İzmit, Kocaeli
There is an increasing energy demand, due to the limitation of fossil oil reserves. In
search of alternative energies, many scientists, pay more attention on the renewable
energy sources because of less pollution, reliability and long-term profit. Fuel cell
technology is an attractive alternative lately for producing electricity. The growth in
fuel cell technology has improved the demand for hydrogen (H2), which is the simplest
and most abundant element [1]. Hydrogen production process and technology, has
been improving and changing but, currently hydrogen is mostly produced from natural
gas and oil fractions, which are still abundant and economically feasible. Nevertheless,
hydrogen production by these methods, produces high amount of carbon monoxide.
Glycerol, which is the by-product of biodiesel production, is non-toxic, non-volatile
and has high energy density. Theoretically, after the transesterification process, 10
kg biodiesel and as by-product, 1 kg glycerol can be produced [2]. Increasing energy
demand will cause the need for clean energy technologies, like biodiesel, and this will
effect glycerol production. By using glycerol for hydrogen production, more effective
and clean energy can be produced. In this study, a reaction prosess is designed and
built in Kocaeli University Chemical Engineering Department Catalyst Investigation and
Development Laboratory (KARGEL) and proper catalyst and reaction conditions are
investigated. With using nickel based catalysts, the most favorable support is found as
CeO2 with % 15 (wt) nickel loading. Besides that, some reaction conditions, like water /
glycerol ratio is also investigated and hydrogen yield is increased with increasing water/
glycerol ratio. The highest hydrogen yield is found as 4,82, with % 15 Ni/ CeO2 catalyst,
water / glycerol ratio of 15 and 650°C.
REFERENCES
[1] Johnston, Technovation, 25 (2005) 569.
[2] Wang, Fuel Processing Technology, 91 (2010) 1812.
50
Oxy-CO2 Reforming of Methane over Al2O3 Supported Nickel
Catalysts prepared by Deposition-Precipitation with urea
Tuba Gürkaynak Altınçekiça, Tugay Pehlivana
a
Chemical Engineering Department, İstanbul University,34320,Istanbul,Turkey
One of the most attractive chemical approaches for the utilization of carbon dioxide
(CO2) and methane (CH4), which are the main components of some natural gas
resources including coal bed gases, could be the catalytic oxy-CO2 reforming of
methane to produce syngas [1]. Noble metal based catalysts exhibit high activities and
stabilities, their limited availabilities and high costs confine their wide spread application
in industry. So nickel (Ni)-based catalyst became commercially more attractive for
the methane reforming processes. But the carbon deposition which causes rapid
deactivation on the Ni based catalysts is one of the important problems associated with
the methane reforming processes. This problem could be minimized by modification of
the catalysts. The oxy-CO2 reforming of methane to produce syngas were tested over
Ni/Al2O3, Ni/ZrO2, Ni/CeO2 and Ni/MgAl2O4 catalysts with various Ni loadings which
were prepared via deposition-precipitation method using precursor of nickel nitrate
and urea [2]. The catalysts were characterized by X-ray powder diffraction analysis
(XRD), H2-temperature-programmed reduction (H2-TPR) and Brunauer Emmett Teller
(BET) analysis techniques. The reforming reactions were carried out using a gas mixture
with a feed ratio of (CH4/CO2/O2/N2=3/1/1/4) and reaction temperatures in the range
700–800 ºC. The activity and stability of the catalyst, carbon deposition, and synthesis
gas (H2/CO) ratio were determined. Among the catalysts evaluated, catalyst with 15
wt.% Nickel content Ni/Al2O3 catalysts revealed the most active catalytic performance
toward combined reforming reactions. In addition, catalyst with 15 wt.% nickel loading
was employed in long term stability test and has shown stable catalytic performance
up to 10 h time on stream without any decrease in methane conversion in the process.
Fig.1 HRTEM micrograph of 15 wt.% Ni/Al2O3 catalysts
Fig.2 Activity Results of Ni/Al2O3 catalysts
Acknowledgement
51
This study was supported by The Scientific and Technological Research Council of Turkey,
Engineering Research Grant Committee (MAG), through project No: 213M381 and by Istanbul
University Research Fund through project No: 49082
References
[1] Hu, Y.H., Ruckenstein, E., 2004, Catalytic conversion of methane to synthesis gas by partial
oxidation and CO2 reforming, Advances in Catalysis, 48, 297-345
[2] Wiley, J., 2009, Synthesis of Solid Catalysts, ISBN: 9783527320400, 111-112
52
Production of 5-Hydroxymethylfurfural by Catalytic Dehydration
of Fructose over SO4/La-TiO2-SiO2
Emre KILIÇ1, Tjeerd Alexander NIJHUIS2, Selahattin YILMAZ1
1
Department of Chemical Engineering, Izmir Institute of Technology, Izmir, Turkey
2
SABIC T&I Chemical, Geleen, The Netherlands
5-hydroxymethylfurfural (HMF) is a valuable intermediate for fine chemicals,
pharmaceuticals and furan-based polymers. It can be produced by acid-catalyzed
dehydration of fructose. In the present study, acidic mesoporous SO4/La-TiO2-SiO2
catalyst prepared by sol-gel method was developed for this reaction. Its titanium and La
content was 6 and 1 wt. %, respectively. The catalyst was sulfated by ammonium sulfate.
With La addition, the sulfur captured by the catalyst increased and thereby its acidity
increased magnificently. Reaction tests were carried out in water-methylisobutylketone
at three different temperatures (110, 160, 200 oC). Different fructose/catalyst weight
ratios (WFr/Wcat= 0.5, 1.0 and 2.0) were also applied.
Activity results showed that SO4/La-TiO2-SiO2 catalyst was very active and fructose was
completely converted in 3 h at 160 and 200 oC. HMF selectivity of 96 % was achieved
at 160 oC. At higher temperature of 200 oC, the selectivity dropped to some extent due
to the secondary decomposition of HMF. Fructose conversion and HMF selectivity was
also affected significantly by fructose/catalyst weight ratio. A complete conversion (100
%) was observed for WFr/Wcat 0.5 and 1. However, activity dropped significantly (from 99
% to 69 %) when WFr/Wcat increased from 1 to 2. This was attributed to the reaction of
fructose with side products instead of adsorption to the catalyst acid sites. In addition,
selectivity to HMF decreased slightly (from 99 to 93% at about 90 % conversion).
53
Catalytic performance of transition metal doped montmorillonite
for biomass hydrolysis
Emir Zafer Hoşgüna, Ebru Tunça, Halit Levent Hoşgünb, Berrin Bozana
Anadolu University, Engineering Faculty, Chemical Engineering Department, Eskisehir.
Bursa Technical University, Engineering Faculty, Chemical Engineering Department, Bursa.
a
b
In recent years, hydrolysis of cellulose with solid catalysts has taken attention by many
researchers. This process is an environmentally friendly technology with overcomes
problems associated with less-environmentally friendly chemicals and product
purification.
Montmorillonite is one of the most common 2:1 type clays. It is widely dispersed on the
earth’s surface which has high hydrothermal stability and large surface area [1].
In this study, hazelnut shells were used as biomass transition metals doped
montmorillonite used as heterogeneous catalyst. The doped montmorillonite catalyst
were prepared by impregnation methods using Cr(NO3)3, CuNO3, Fe(NO3)3, Co(NO3)2
and Zn(NO3)2. Metal nitrates (10 wt%) were dissolved in an ethanol-water mixture (5050%) and montmorillonite was added into the solution and mixed for 24 h. Collected
clay was washed with DI water and dried under vacuum at 40°C. Catalytic hydrolysis
were carried out in a high temperature-high pressure stainless steel reactor (Parr, USA)
reactor. Reaction conditions were 180°C, 2 hr and 1/100 catalyze/biomass ratio. The
solution was kept liquid under N2 atmosphere (10 bar). At the end of the treatment,
the treated slurry was collected and filtered using filter paper to separate the solid and
liquid fractions for further analysis. Compositions of liquid products were analyzed by
high-performance liquid chromatography (HPLC) [2].
All the catalysts synthesized in this study were effective on the furfural and HMF yield
and selectivity from the biomass. Cr-MMT was the most effective one, followed by CuMMT, Zn-MMT and Fe-MMT. 30.38 mg furfural and 1.96 mg HMF was produced per
gram of the biomass in the presence of the Cr-MMT catalyst.
Acknowledgement
This study was supported by Anadolu University Scientific Research Projects Commission under the
grant no: 1502F065
References
[1] Tong, D. S., Xia, X., Luo, X. P., Wu, L. M., Lin, C. X., Yu, W. H., & Zhong, Z. K. (2013).
Catalytic hydrolysis of cellulose to reducing sugar over acid-activated montmorillonite catalysts.
Applied Clay Science, 74, 147-153.
[2] Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J. ve Templeton, D. (2006), “Determination
of sugars, byproducts, and degradation products in liquid fraction process samples,” National
Renewable Energy Laboratory, Golden, CO.
54
Parametric investigation of glycerol reforming in a wall-coated
microchannel reactor
Sinan Koc, Ahmet Kerim Avci
Department of Chemical Engineering, Bogazici University, Bebek 34342 Istanbul/Turkey
Conventional production of biodiesel via transesterification of animal-based or
vegetable oils is known to cause an oversupply of glycerol as a byproduct. A possible
solution for removing excess glycerol involves efficient conversion of glycerol to H2.
This conversion requires high temperatures and external energy demand, both of which
depend strongly on the catalyst type and reactor geometry. Microchannel reactors are
known to enable high heat transfer rates, and fast and homogeneous distribution of
external heat to the catalyst bed, favoring its efficient utilization.
The work is aimed to investigate non-oxidative (GSR) and oxidative glycerol steam
reforming (OGSR) over Ni-based catalysts in a microchannel reactor. The effects of
reaction temperature (773-873 K), molar inlet steam-to-carbon (S/C=3-6) and carbonto-oxygen (C/O=0.75-2.25) ratios are studied. The reactor is composed of a Ni coated
FeCrAlY plate that is inserted into a µ-EDM machined cylindrical steel housing to
give a single microchannel (0.75x4x20 mm). Coated FeCrAlY plate is obtained by first
preparing powdered catalyst (5 and 10% Ni/Al2O3) and then by mixing it with deionized
water to form slurry, which is coated on oxidized FeCrAlY. Product analysis is done via
two on-line GCs on MS-5A and Porapak Q columns.
Results show that glycerol conversions and product yields obtained in OGSR are
notably higher than those of GSR. Decreasing C/O ratio improves conversion, but
decrease H2 yield. Changing S/C ratio affects product distribution via water-gas shift. H2
yield is improved S/C, which is found to be optimal between 4 and 5; higher values lead
to lower conversions due to possible Ni sintering and/or reoxidation of Ni sites. In all
cases, coking is detected, but found to be much less severe in OGSR. Increasing metal
loading gives only a minor increase in conversion due to better Ni dispersion in the 5%
case, as observed from SEM-EDX analysis.
55
BIODIESEL PRODUCTION FROM MODEL WASTE VEGETABLE OIL
BY USING ZIRCONIUM SULFATE CATALYST
Melike İmge ŞENOYMAKa, Oğuzhan İLGEN a,b
a
Chemical Engineering Department, Kocaeli University, 41380, Kocaeli, Turkey
b
Alternative Fuels R&D Center, Kocaeli University, 41040 Kocaeli, Turkey
Biodiesel is defined as mono-alkyl-esters of long chain fatty acids derived from
renewable and natural resources like vegetable oils and animal fats [1, 2]. In biodiesel
production process, the most important disadvantage is high cost of feedstock oils. For
this reason, many studies have been done for using cheaper feedstocks such as nonedible oils, animal oils or waste cooking oils [3]. Since the cheaper oil sources contain
high free fatty acid, acid catalysts that catalyzed transesterification and esterification
reactions simultaneously are more suitable [4]. In this study, zirconium sulfate was used
as a heterogeneous acid catalyst because of its high catalytic activity, low toxicity, low
cost and easy handling [5]. Waste vegetable oil was modeled by adding 6 wt.% of oleic
acid as free fatty acids into sunflower oil. In the course of biodiesel production, effects of
some reaction parameters such as reaction time, reaction temperature and reusability
of catalyst were investigated. The highest fatty acid methyl ester (FAME) yield of 86 %
was obtained under reaction conditions of 115°C reaction temperature, 4 h reaction
time, 9:1 methanol/oil molar ratio and 3 wt.% catalyst amount.
References
[1] Mohapatra S.B., Das P., Swain D., Satapathy S., Sahu S. R., A Review on Rejuvenated Techniques
in Biodiesel Production from Vegetable Oils, International Journal of Current Engineering and
Technology 6 (2016) 100-111.
[2] Sirisomboonchai S., Abuduwayiti M., Guan G.,Samart C., Abliz S., Hao X., Kusakabe K.,
Abudula A., Biodiesel production from waste cooking oil using calcined scallop shell as catalyst,
Energy Conversion and Management 95 (2015) 242-247.
[3] Z. Wen, X. Yu, S. Tu, J. Yan, E. Dahlquist, Biodiesel production from waste cooking oil catalyzed
by TiO2–MgO mixed oxides, Bioresource Technology 101 (2010) 9570–9576.
[4] O. Ilgen, Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification
with methanol by using Amberlyst 46 as a catalyst, Fuel Processing Technology 124 (2014)
134-139.
[5] Juan J., Zhang J., Yarmo M., Study of catalysts comprising zirconium sulfate supported on a
mesoporous molecular sieve HMS for esterification of fatty acids under solvent-free condition,
Applied Catalysis A, 347 (2008) 133-141.
56
ESTERIFICATION OF CETYL ALCOHOL AND PALMITIC ACID OVER
W AND Zr CONTAINING ACIDIC CATALYSTS
Vahide Nuran Mutlua, Selahattin YILMAZa
a
Izmir Institute of Technology, Chemical Engineering, Izmir Instıtute of Technology Chemical Eng.
Department Urla, Izmir Turkey
Esters of fatty acids and alcohols are used as raw materials for emulsifiers, oiling agents
and surfactants in different industrial areas. Cetyl palmitate is one of the most important
cetyl esters for cosmetics industry. In the present study, it was aimed to develop active,
selective and reusable heterogeneous catalysts for esterification of cetyl alcohol by
palmitic acid. For this purpose, Zr incorporated SBA-15 was prepared by hydrothermal
synthesis. Silylation of Zr-SBA-15 was performed to see the effect of hydrophobicity of
the catalyst. WO3 loading onto the Zr-SBA-15 was also performed by incipient wetness
impregnation. Moreover, WO3-ZrO2 catalyst was prepared by co-precipitation with two
different contents of WO3 (15 wt% and 20 wt%). The catalysts were characterized by
XRD, Raman, BET, NH3-TPD and FTIR. The reaction tests were carried out in mesitylene
under reflux conditions within 6 h reaction time. Zr-SBA-15 catalyst which had the
highest amount of Brønsted acid sites gave maximum cetyl palmitate yield (See Table 1).
This catalyst retained its activity up to 3 reuse cycles without significant loss of activity.
Table 1 Initial rate of disappearance and conversion of cetyl alcohol and yield of cetyl palmitate over
different catalysts
* r0/TA is defined as r0x105 per total acidity
This study was founded by TUBITAK as project number 112M701. Their support is
gratefully acknowledged.
References
[1] K. Mantri, K. Komura, Y. Sugi, Green Chemistry 7, (2005), 677-682
[2] A. Sakthivel, K. Komura, Y. Sugi, Ind.Eng.Chem.Res. 47, (2008) 2538-2544
57
DESIGN AND CHARACTERIZATION OF SELECTIVE CO2
ADSORBENTS
Burcu Acara, Burcu Selen Çağlayana,b, A. Erhan Aksoylu,a
a
Boğaziçi University, Department of Chemical Engineering, 34342, Istanbul, Turkey
Advanced Technologies R&D Center, Boğaziçi University, 34342, Istanbul, Turkey
b
Nearly 40% of CO2 in the atmosphere is emitted by fossil fuel based power production
plants (coal, oil, gas). In abatement of CO2 emission to the atmosphere originating
from these units, carbon capture and sequestration technologies (CCS) have a high
potential. As CCS currently is an expensive process, cost effective CCS options need to
be developed. Adsorption is taught as one of the most promising approach due to the
low energy requirement, cost advantage, and ease of applicability over a relatively wide
range of temperatures and pressures [1].
The aim of this study is to design and develop AC-based CO2 adsorbent(s) having both
high and stable CO2 adsorption capacity, and ability to adsorb CO2 selectively from CO2CH4 mixture. In this context, a commercial activated carbon, Norit ROX, was oxidized
by air and HNO3, and two series of adsorbents, AC8 and AC9 series, respectively, were
prepared on those oxidized ACs by K2CO3 impregnation followed by calcination at
various temperatures. Adsorption/selective adsorption tests were conducted for
0-1000 mbar pressure range under 50 ml/min gas flow rate at room temperature (RT),
120 °C and 200 °C for pure CO2, pure CH4 and their mixtures, 50% CO2-50% CH4 and
10% CO2-90% CH4. Adsorbent with the best CO2/CH4 selectivity results was further
tested for 0-5000 mbar pressure range at RT. While pressure icrease had a positive
effect on adsorption, temperature increase had a negative effect on adsorbed CO2 and
CH4 amounts.The experimental adsorption isotherm data were fitted to Langmuir,
Freundlich and Dubinin-Radushkevich (D-R) models and D-R model was found to be
the most successful one in explaining CO2 and CH4 adsorption behaviors of AC samples.
Pseudo-first order and pseudo-second order kinetic models are fitted to kinetic data.
Pseudo-first order kinetic model was more successful in explaining both CO2 and CH4
adsorption kinetics at RT.
References
[1] B. S. Caglayan, A. E Aksoylu, Journal of Hazardous Materials 252-253 (2013) 19-28.
58
Novel Hybrid Perovskite Catalysts For DeNOx Applications
K.E. Ercana, Z. Saya, E.I. Vovka,b, G. Pantaleoc, L. Liottac, A. Veneziac, and E. Ozensoy*c
Department of Chemistry, Bilkent University, 06800 Ankara, Turkey
Boreskov Institute of Catalysis, 630090, Novosibirsk, Russian Federation
c
CNR-Institute for the Study of Nanostructured Materials (ISMN), 90146, Palermo, Italy
a
b
Air pollution due to the emission of toxic gases is a serious threat for human health.
Recently, it was reported that perovskite based De-NOx catalysts can be used as an
alternative to the high-cost Pt oxidation catalysts [1,2]. In this work, a new generation
of hybrid perovskites were designed in the form of LaCoxMn1-xO3 by varying Co and
Mn loadings (x=0.1-0.9) in an attempt to fine-tune the thermal stability and catalytic
activity of the catalysts as shown in Figure 1. NOx adsorption and release properties
of hybrid perovskites were analyzed via TPD. Figure 2 shows the NO(g) desorption
channels of the investigated materials during nitrate decomposition indicating that
NO desorption characteristics are strongly influenced by Mn/Co ratio in the catalytic
formulation. Co-rich hybrid perovskites can store and release a significantly higher
amount of NOx where LaCo0.8Mn0.2O3 catalyst has the greatest amount of NOx storage
as compared to all other perovskites.
Figure 1: Material design strategy for the
Figure 2: NO(g) TPD profiles of H2 pre-treated perovskites
synthesis of hybrid perovskites.
References:
[1] C. Kim, G. Qi, K. Dahlberg, W. Li, Science (2010) 1624–1627,327 (2010)
[2] Z. Say, M. Dogac, E.I. Vovk, Y.E. Kalay, C.H. Kim, W. Li, E. Ozensoy, Appl. Catal. B: Environ.
154-155, 51 (2014)
59
NH3 Uptake Behavior of a Commercial Cu-Zeolite Monolithic
Catalyst for the NH3-Selective Catalytic Reduction of NOx
Selmi Erim Bozbağa, Feyza Gökalilerb, Gökhan Hisarb, Can Erkeya,c
Koç University, Chemical and Biological Engineering Department, 34450, Sarıyer, Istanbul,
Turkey.
b
Ford-Otosan Sancaktepe Engineering Center, Akpınar Mh. Hasan Basri Cd. No:2 34885
Sancaktepe, İstanbul, Turkey
c
Koç University TÜPRAŞ Energy Center (KUTEM), Koç¸ University, 34450 Sarıyer, Istanbul, Turkey.
a
Selective Catalytic Reduction of NOx with NH3 is a widely used technology for the
engine aftertreatment of diesel vehicles in the presence of excess oxygen and water.
Cu ion-exhanged zeolites with chabazite (CHA) structure have recently become the
catalyst of choice because of its high NOx conversion performance at a relatively
large temperature range and good hydrothermal stability [1, 2]. The recent and most
consistent reaction scheme for NH3-SCR of NOx on Cu/CHA suggests the reaction of
the adsorbed NH3 with adsorbed N=O or adsorbed nitrite species on Cu+ and Cu2+ sites,
respectively [3]. Therefore, the fundamental understanding of NH3 adsorption on the
catalyst is the first and a very important step towards elucidating the reaction kinetics
for the development of a reactor model. In this study, we used the synthetic gas bench
heterogeneous catalysis setup we have installed in Koç University and investigated
the adsorption of NH3 on Cu/CHA using the Temperature Programmed Desorption
of NH3 (TPD-NH3) in the absence and presence of O2 and H2O at a NH3 saturation
temperature range of 150-400 oC. TPD curves indicated three desorption sites at 343,
471 and 560 oC associated with NH3 chemisorption when the adsorption was carried
out at 150 oC in the absence of O2 and H2O. The peak at the 343 oC gradually degraded
as the saturation temperature increased or when O2/H2O was present in the saturation
stream. The amount of chemisorbed NH3 stored in the catalyst decreased when the
saturation temperature increased from 150 to 400 oC, respectively. The presence of 8%
O2 and 5% H2O in the NH3 saturation stream caused a decrease in the NH3 uptake from
6 to 100% when the saturation temperature increased from 150 to 400 oC, respectively,
due to the oxidation of NH3.
References
[1] J. H. Kwak et al., J. of Catalysis 275 (2010) 187.
[2] Supriyanto et al., Applied Catalysis B: Environmental 163 (2015) 382.
[3] T. V. W. Janssens et al., ACS Catalysis 5 (2015) 2832.
60
Sulfur-Tolerant BaO/ZrO2/TiO2/Al2O3 Quaternary Mixed Oxides for
DeNOx Catalysis
Z. Say[a,c], O. Mihai[b], M. Tohumeken[a], L. Olsson[b], E. Ozensoy[a
Chemical Reaction Engineering and Competence Centre for Catalysis, Chalmers University of
Technology, SE-412 96 Göteborg, Sweden
[c]
Chemistry Laboratory Directorate, Turkish Standardization Institute, 06800 Ankara, Turkey
[a]
[b]
Advanced quaternary mixed oxide materials in the form of BaO/Al2O3/ZrO2/TiO2
which were functionalized with Pt active sites (i.e. Pt/BaO/AZT) were synthesized and
structurally characterized via XRD and BET in comparison to a conventional Pt/20BaO/
Al benchmark NSR/LNT catalyst. Interaction of these catalyst surfaces with SOx and
NOx gases were monitored via spectroscopic techniques such as in-situ FTIR and
TPD. There exists a delicate trade-off between NOx Storage Capacity (NSC) and sulfur
uptake/poisoning which is strongly governed by the BaO loading/dispersion as well as
the surface structure and acidity of the support material. Flow reactor measurements
performed under realistic catalytic conditions show high NOx activity for Pt/8BaO/AZT
and Pt/20BaO/AZT catalysts at 473 and 573 K. After sulfur poisoning and subsequent
regeneration at 773 and 973 K, Pt/8BaO/AZT and Pt/20BaO/AZT surpassed NOx
catalytic performances of all other investigated materials including the conventional
Pt/20BaO/Al benchmark catalyst at 473 and 573 K [1-9].
Figure 1: FTIR spectra related to SOx release properties of sulfur-poisoned (a) Pt/AZT, (b) Pt/8Ba/AZT,
(c) Pt/20Ba/AZT and (d) Pt/20Ba/Al in the presence of H2(g).
References
[1] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Topics in Catalysis 56 (2013) 950.
[2] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Appl. Catal. B: Environ. 142-143 (2013) 89.
[3] Z. Say, M. Tohumeken, E. Ozensoy, Catalysis Today 231 (2014) 135.
[4] Z. Say, M. Dogac, Y.E. Kalay, C.H. Kim, W. Li, E. Ozensoy, Appl. Catal. B: Environ.154-155
61
(2014) 51.
[5] Z. Say, M. Tohumeken, E. Ozensoy, Catalysis Today Catalysis Today 10.1016/j.
cattod.2015.12.013
[6] G.S. Senturk, E.I. Vovk, Z. Say, A.M. Soylu, V.I. Bukhtiyarov, E. Ozensoy, Catalysis Today 184,
54 (2012).
[7] Z. Say, O. Mihai, M. Tohumeken, K.E. Ercan, L. Olsson, E. Ozensoy, ChemSusChem (2016)
submitted
[8] M. Dogac, Z. Say, E.I. Vovk, C.H. Kim, E. Ozensoy, Topics in Catalysis (2016) submitted.
[9] Z. Say, O. Mihai, M. Tohumeken, K.E. Ercan, L. Olsson, E. Ozensoy, ChemSusChem (2016)
submitted
62
Development of CuOx/nr-TiO2 Catalysts for CO2 abatement
Murat Efgan KİBARa,b, Gizem GÜRGÜRa,b, Ayşe Nilgün AKINa,b
Kocaeli University, Department of Chemical Engineering, 41380, Kocaeli
Kocaeli University, Alternative Fuels Research and Development Center, 41040, Kocaeli
a
b
The amount of greenhouse gases has been increasing with the energy consumption.
Uncontrolled CO2 release is the first actor of global warming. Therefore the reduction of
CO2 emission supports to produce more efficient energy systems. CO2 can be used and/
or reduced by storage, artificial photosynthesis, active reactant, catalytic CO2 reactions
and etc. Photocatalytic reactions exhibit more moderate reaction conditions with
respect to thermal reactions [1,2]. In the present study, the catalytic reaction conditions
are investigated between sodium metaborate solutions and CO2. Nano rod (nr) titania
(TiO2) are synthesized from commercial TiO2 as a support material and the activities
of the cupper are investigated for the photocatalytic reactions. The conversions were
calculated due to the online observation of feed and output stream concentrations.
The reactions performed in a semi-batch quartz reactor with the constant flow rate of
CO2 and also with 5% and 10% CuOx/nr-TiO2 catalysts. The catalysts were charecterised
with the analytical tecniques of BET, x-ray powder diffraction and transmission electron
microscopy. Nano rod formation is given in Figure 1. According to the results, CuOx/nrTiO2 has been found as an active catalyst for CO2 abatement with sodium metaborate
solution.
Figure 1. TEM image of CuOx/nr-TiO2 catalyst
References
[1] Tahir, M., NorAishah S. A., Renewable and Sustainable Energy Reviews, 25 (2013) 560-579.
[2] Jeyalokshmi,V., Rajalokshmi, K., Res Chem Intermed., 39 (2013) 2565-2602.
63
Carbon Aerogel Supported Platinum-Copper Nanoalloys Using
Supercritical Deposition
Şansım Bengisu BARIMª, Ezgi Erdemª, Selmi Erim Bozbağª, Rıza Kızılelb, Mark Aindowc,
Haibo Yuc, Can Erkeya,b
Department of Chemical and Biological Engineering, Koç University, 34450, Sarıyer, Istanbul,
b
Koç University Tüpraş Energy Center (KUTEM), Koç University, 34450, Sariyer, Istanbul
c
Department of Materials Science and Engineering, Institute of Materials Science, University of
Connecticut, 06269, United States
a
Supercritical deposition method is attracting increasing attention for preparation of
supported bimetallic nanoalloys because it provides good control of metal loading,
particle size and homogeneous distribution of bimetallic nanoparticles on the substrate
surface. The technique involves dissolution of organometallic compounds in the
supercritical fluid and exposure of a porous substrate into this mixture followed by
the adsorption of metallic precursors onto the substrate. Precursors on the surface are
then converted to their metal forms via different routes. Carbon supported Pt is the
commercial catalyst for polymer electrolyte membrane fuel cell (PEMFC) electrodes,
however; its high cost constitutes a big obstacle for the commercialization of PEMFCs.
Therefore, research efforts are directed to reduce the amount of platinum while
maintaining the activity by developing alloys of Pt with cheap metals. In this study,
the applicability of supercritical deposition was investigated for preparation of carbon
aerogel (CA) supported Pt-Cu- nanoalloys for use as electrocatalysts for PEMFCs. For
this purpose, dimethyl(1,5-cyclooctadiene) platinum(II) (Pt(cod)me2) was used as the
platinum precursor and copper(II)trifluoroacetylacetonate (Cu(tfa)2) was used as the
copper precursor. Single adsorption isotherms of both precursors were determined
and from single adsorption isotherms binary adsorption isotherms of Pt(cod)me2Cu(tfa)2-CA system were determined using Ideal Adsorbed Solution Theory (IAST).
Reduction of adsorbed precursors were done at 200 oC under flowing hydrogen.
Catalysts were then annealed at 600 oC. STEM images and XRD data showed that Pt-Cu
nanoparticles were alloys and the average size of the particles was around 3-4 nm with a
narrow particle size distribution. Electrochemical activity of the prepared catalysts were
investigated using cyclic voltammetry which were conducted in a conventional three
electrode electrochemical cell assembly containing 0.1 M HClO4 as electrolyte.
64
Enviromental Friendly Latent Ruthenium Metathesis Catalysts
for the Synthesis of Nano-ROMP Polymers
Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa
a
Hacettepe University, Department of Chemistry, 06800, Beytepe, ANKARA
Scheme 1. Ruthenium indenylidene complexes bearing protonable side groups
Olefin metathesis is a useful synthetic method to prepare complex molecular structures
in an efficient manner[1]. Due to the tremendous interest in olefin metathesis, recent
studies focus on the development of latent and more environmentally friendly
metathesis catalysts [2]. Latent catalysts are of great importance in polymer chemistry,
since the latency of the catalyst allows the efficient mixing of the catalyst in monomer
without any polymerization reaction occurring at ambient temperatures [3].
In this study, we developed two novel ruthenium indenylidene Schiff base catalysts,
bearing morpholine (Ru-1) and tertiary amine (Ru-2) functionality (Scheme 1). Ru-1
and Ru-2 are latent and inactive towards olefin metathesis reactions under normal
conditions and can be activated on demand by introduction of HCl to the reaction
media. Emulsion ring opening metathesis polymerization (ROMP) reactions were
carried out in aqueous media using non-ionic surfactants and nano-sized polymeric
particles (25-75 nm) were obtained. Molecular weights (Mn) of ROMP polymers
were controlled between 90-280 kDa by varying HCl/Ru (mol/mol) ratio during the
activation step. In addition, both catalysts exhibit high silica gel affinity. The metal
concentration of the final product can be reduced to 2 ppm from 500 ppm by simple
silica gel filtration.
References
[1] T.M. Trnka, R.H. Grubbs, Acc Chem Res, 34 (1) (2001), 18–29
[2] A. Szadkowska, K. Grela, Curr Org Synth, 12 (2008), 1631–1647
[3] A. Leitgeb, M. Abbas, A. Poater, L. Cavallo, C. Slugovc, Catal Sci Technol, 2 (2012), 1640–1643
65
KINETIC AND MECHANISTIC FEATURES OF CARBON DIOXIDE
REFORMING OF METHANE OVER Co–Ce/ZrO2 CATALYSTS
Aysun İpek Paksoyª, Cansu Yassı Akdağª, Burcu Selen Çağlayanb,ª. Erhan Aksoyluª
a
Bogazici University, Department of Chemical Engineering, 34342, Istanbul, TURKEY
Bogazici University, Research and Development Center, 34342, Istanbul, TURKEY
b
Carbon dioxide reforming of methane (CDRM) is an environmentally friendly catalytic
process since it utilizes two thermodynamically stable greenhouse gasses, CO2 and CH4,
to produce synthesis gas. The low H2/CO product ratio is also preferable for further
processes like Fischer-Tropsch synthesis. However, highly endothermic nature of CDRM
imposes high reaction temperatures and this may cause coking and/or metal sintering.
[1] It is also reported that this is a slow reaction involving long residence times [2].
Therefore, to compete with the other reforming routes in commercial production, the
economical impediments of the process should also be overcome. Thus, mechanistic
features of the reaction need to be revealed.
The previous studies have shown that Ce-doped Co/ZrO2 catalysts perform high
activity and have a very limited activity loss [1]. This study aims to determine the
kinetic behavior of CDRM over 5%Co-2%Ce/ZrO2 and 10%Co-2%Ce/ZrO2 catalysts
as a function of temperature and partial pressures of CH4, CO2, CO and H2. In this
context, power-law type rate expressions were obtained for both catalysts. Then, the
experimental data were fit to mechanistic rate expressions, and the model parameters
were determined. The reaction orders with respect to CH4 were estimated to be higher
than that for CO2 in the power type rate laws of both catalysts. An inhibitory effect of
H2 introduction to the feed was also noted. The model that best fitted to the CDRM
kinetics on 5%Co-2%Ce/ZrO2 catalyst was expressed as the one based on an Eley-Rideal
type mechanism with the reaction of adsorbed CO2 with CH4 in the gas phase as rate
determining step. For 10%Co-2%Ce/ZrO2 catalyst, the model derived from LangmuirHinshelwood type mechanism with CH4 dissociation as the rate determining step gave
the lowest squared error.
References:
[1] A. I. Paksoy, B. Selen Caglayan, A. E. Aksoylu, Applied Catalysis B: Environmental, 168 (2015)
164-174.
[2] Y. Kathiraser, U. Oemar, E. T. Saw, Z. Li, S. Kawi, Chemical Engineering Journal, 278 (2015)
62–78.
66
Computational (DFT) and Experimental (FTIR-DRIFT)
Investigation of CO2 Activation on ZrO2
A. Uzuna, A. İ. Paksoya, V. Çimenoğlub, A. E. Aksoylu*,a
b
Siemens Healthcare, Kartal, Istanbul, Turkey
a
Carbon dioxide reforming of methane (CDRM) consumes carbon dioxide and methane,
two thermodynamically stable greenhouse gasses, and produces synthesis gas. CO2
utilization makes dry reforming in attractive way to avoid global warming. CDRM process
has been attracted widespread attention of many researchers considering the fact that
its product has H2/CO=1, which is suitable for production of valuable hydrocarbons
and oxygenated compounds through following reactions such as Fischer-Tropsch
process. Supports like ZrO2 play a crucial role in stable activity of CDRM catalysts by
activating CO2 to yield surface oxygen which is responsible for cleaning surface carbon
forms during reaction [1]. Though oxygen formation and transfer mechanism has been
used in many research papers for explaining CDRM process, there has been less work
merely focus on CO2 activation on ZrO2.
In the current study, computational and experimental findings were used in a combined
fashion to understand the details of the CO2-ZrO2 interaction. In the experimental
part, CO2 adsorption on ZrO2 was analyzed by FTIR-DRIFT, and the results confirmed
ZrO2-CO2 interaction via detection of CO as a product when CO2 adsorption on
ZrO2 was conducted. Additionally, formation of different surface groups was noted.
In computational part, the adsorption of CO2, CO and O on the stoichiometric
m-ZrO2(11) was explored using DFT calculations on periodic models. DFT simulations
clearly showed that CO2 interacts with stoichiometric m-ZrO2(11), but this does not
yield C-O bond breakage, and there is weak CO adsorption on surface sites of the
ordered m-ZrO2(11). As the DFT results eliminated the surface oxygen production
on ordered m-ZrO2(11) sites, the evaluation of experimental and computational
results indicated that CO2 activation yielding surface oxygen occurs on defect sites of
m-ZrO2. DFT results on O adsorption also revealed that oxygen mobility is possible on
m-ZrO2(11) surface.
References:
[1] A. I. Paksoy, B. Selen Caglayan, A. E. Aksoylu, Applied Catalysis B: Environmental, 168 (2015)
164-174.
67
Performance test of monolithic Ni-based catalyts for carbon
dioxide reforming of methane
Aybüke Lebaa, Ramazan Yıldırıma
a
Department of Chemical Engineering, Boğazici University, 34342 İstanbul, TURKEY
The utilization of carbon dioxide and methane together as a reforming process to
synthesis gas has been received a great attention for a few decades since it has been
considered as a promising solution for global warming. From the industrial point of
view, the demand of an effective and economic catalyst is still a crucial issue. Ni-based
catalysts have been seemed to be a good alternative for the process as having low cost
and remarkable activity; however, stability is still a major problem [1]. Therefore, great
efforts to diminish the deactivation and to extend its industrial application are ongoing.
In this study, Ni-based catalysts were evaluated in the monolithic form which is believed
to provide excellent heat transfer [2]. The cordierite monoliths were wash-coated with
various supports such as MgO, SiO2 and CeO2 to see support effect on this form; and
then were co-impregnated with Ni and Co active metals. The performance test of the
catalyst was conducted in a fixed bed quartz reactor (I.D.=10.00mm) at the temperature
interval of 873–1173 K and at 1 atm. A gas hour space velocity (GHSV) of 42,000mL/
hg-catalyst was used with CH4/CO2 feed ratios of 1 to obtain a product H2/CO ratio of
1. N2 was also used as an internal standard. The results showed that monolithic form of
the catalyst has a positive effect on the performance of the catalyst, such as in the case
of MgO, where CH4 conversion and CO2 conversion at 800°C were increased from 83%
and 90% to 90% and 94%, respectively, comparing with the granule form.
References
[1] C. Li et al., Fuel Processing Technology, 140 (2015) 39-45.
[2] M.P. Kohn et al., Applied Catalysis B, 94 (2010) 125-133.
68
Structure-performance relationships in supported nickel
catalysts for hydrogen production from ammonia
İbrahim Şahina, Alper Uzuna
Department of Chemical and Biological Engineering, Koç University, 34450 Sariyer, Istanbul,
Turkey
a
Hydrogen can be produced in on-board applications via ammonia decomposition with
no COx emissions. Ruthenium based supported catalysts were initially studied for this
reaction because of their superior performance; however, there is a need for a cheaper
alternative due to high price and limited availability of ruthenium. Thus, in this study, we
focus on nickel based catalysts as cheap alternatives. We have elucidated the structureperformance relationships of on these cheap counterparts for hydrogen production
by ammonia decomposition. These relationships were studied by changing nickel
nanoparticle size systematically on various metal-oxides, such as SiO2, Al2O3, MgO, TiO2,
CeO2, La2O3, SBA-15, and MCM-41 covering a variety of surface electronic structures
ranging from a point of zero charge of pH = 2 to 11.
Figure 1. Arrhenius plots for the reaction rates of tested catalysts measured at differential conversion.
Data show that hydrogen production rate is controlled by metal nanoparticle size; but
the support’s surface acidity is the dominant factor. As the surface basicity increases, the
rate of hydrogen production increases significantly. Results offer valuable information
towards the design of Ni-based catalysts as cheap alternatives to Ru-based counterparts.
This study is supported by TUBITAK under 1003 Program (Project number: 213M028).
A.U. acknowledges the BAGEP Award of the Science Academy, Turkey.
69
The Effects of Reaction Parameters on Mn/Na2WO4/SiO2 Catalyst
for Oxidative Coupling of Methane
Hasan Özdemira, M.A. Faruk Öksüzömera, M. Ali Gürkaynaka
a
Department of Chemical Engineering, Istanbul University, Avcilar/Istanbul, 34320, Turkey
Oxidative coupling of methane (OCM), which produces ethane and ethylene from
methane directly, attracted considerable attention over decades [1]. However, it has
not been possible to design a catalyst that could provide higher C2 yields than 27%
for the commercialization of this process because of the thermodynamic and kinetic
constraints [2]. Many catalysts have been developed for OCM reaction and amongst
them, Na2WO4/MnO2/SiO2 is the most investigated catalyst in the literature and its
OCM activity and selectivity is quite remarkable. However, there are few reports that
examined the influence of reaction conditions on Na2WO4/MnO2/SiO2 catalyst and
there is no work about the influence of N2O as an oxidant.
Considering these facts, it was aimed to investigate the influence of reaction parameters
such as oxidant type, CH4/O ratio, GHSV and temperature on 2(wt%)Mn/5(wt%)
Na2WO4/SiO2 catalyst for OCM reaction. Activity tests showed that high C2 yields
could be obtained at low CH4/O ratios and contact time independent of the oxidant
type (O2 or N2O) and reaction medium within the selected range of the parameters.
Continuous increase in temperature enhanced the C2 yield especially when N2O was
used for the gas phase reactions. However, the highest C2 yield (16.4%) was obtained
with the catalyst at CH4/O=1, 7500 L kg-1 h-1 and 780°C using O2 as an oxidant and
11.5% at 820°C with the use of N2O. Thus, the optimum temperature depends on
the type of oxidant and catalyst use. Obtained results also indicated that, the catalyst
activity towards O2 dissociation is well but not for N2O decomposition. O2 is more
efficient than N2O but the latter is more selective than the former. 2Mn/5Na2WO4/SiO2
was found to be quite stable during the stability tests performed with both oxidants
under the optimum conditions.
References
[1] J.H. Lunsford, Catal Today, 63 (2000) 165-174.
[2] R. Ghose, H.T. Hwang, A. Varma, Appl Catal a-Gen, 472 (2014) 39-46.
70
Schiff Base complexes on bleach catalyst for the real industrial
applications
Ertug Yildirima,S. Zeki Yildiza, Okan Yuzuakb, Idil Yilmaz Yalinalpb, Nihat Toslub
Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYATURKEY
b
Hayat Holding, Hayat Road, No:2, 41000, KOCAELI-TURKEY
a
Schiff base chemistry is played an important role in the development of coordination
chemistry due to forming complexes with most transitions metals having wide
applications in chemical industry as catalysts [1]. One of the most important
approaches in the chemical industry concerning with the oxidation reactions is the
bleaching process [2]. Oxidative bleach processes are great importance for the pulp
and paper production, textile pre-treatment, waste water treatment and industrial and
domestic laundry processes [3]. Oxidation catalysis is used to increase the performance
of hydrogen peroxide in laundry bleach applications [4].
Bleach activator systems, such as N,N,N’,N’-tetraacetylethylenediamine (TAED), have
been developed and are applied in many laundry detergents. However, bleach catalyst
provide cost-effective, energy saving and environmentally friendly bleach systems
recently [5].
So, in this study the preparation of manganese and cobalt complexes was performed by
using MnCl2. 4H2O and CoCl2.6H2O salts in basic condition for bleach catalysis. FT-IR,
UV–vis spectra were applied to characterize the prepared compounds. The degradation
of Morin dye characterizes the wine stains. The degradation progress in the detergent
characteristic has been examined using online spectrophotometric method (OSM). It
was found that the prepared catalysts exhibited better bleaching performance at 25 °C
than to that of TAED.
References:
[1] Z. Liang, Z. Liu, L. Jiang, Y. Gao, Tetrahedron Lett. 48 (2007) 1629.
[2] J.I. Kroschwitz, M. Howe-Grant Kirk-Othmer, Encyclopedia of Chemical Technology, 4th ed.,
Wiley, New York, 1991.
[3] H. Offermanns, G. Dittrich, N. Steiner, Chemie in Unserer Zeit 34 (2000) 150.
[4] Ranold Hage, Achim Lienke, Angew. Chem. Int. Ed. 45 (2006) 206–222.
[5] G. Reinhardt, M.Loeffler, Tenside Surfact. Deterg. 34, 1997,404.
71
CHARACTERIZATION OF CATALYTIC CONVERTER
Yiğit Türea, Emre Gürlekb, Nurcan Çalış Açıkbaşa, Şeref Soylub and Türker Güdüc
Bilecik Şeyh Edebali University, Metallurgical and Materials Science Engineering Department,
11230, Bilecik
b
Bilecik Şeyh Edebali University, Mechanical and Manufacturing Engineering Department, 11230,
Bilecik
c
TOFAŞ Türk Otomobil Fabrikası A.Ş., 16369, Bursa
a
In this study, the analyses of a commercially available oxidation catalyst (two way
catalytic converter) which was obtained from TOFAŞ A.Ş., were conducted in order
to determine manufacturing process, chemical composition and phase analysis by
several characterization methods, mainly optical microscopy, scanning electron
microscopy (SEM) and x-ray diffraction (XRD). Macrostructural observations by
optical microscopy showed that structure type was honeycomb and dimensions of
cells and frame thickness were 1011x997.4 µm and 116.35 µm, respectively and
shaping technique was extrusion. SEM (SEM-SE-EDX) was used for elemental analysis
and size measurements of coating materials. The results showed that three layers of
coating material existed and included carbon, oxygen, aluminium, silicon, titanium and
cerium. The average thickness of each of layer was 25 µm. XRD analysis showed that the
main phase was Cordierite.
72
POSTER
PRESENTATIONS
(Abstracts)
73
POLYANILINE COATING ON MODIFIED CARBON PASTE ELECTRODE
TO CONSTRUCT AMPEROMETRIC GLUCOSE BIOSENSOR
A.Ebru AYDIN, Gul OZYILMAZ, Serbay BUCAK, Nureddin ÇOLAK, Ali Tuncay OZYILMAZ
Mustafa Kemal University Faculty of Art and Science, Department of Chemistry,31000, Hatay,
Turkey
Carbon paste electrode (CPE) has been shown a convenient type of working
electrode/substrate for such electropolymerization and many studies regarding
electropolymerization on the surface of CPE were done [1]. In this study, amperometric
biosensor construction was carried out by immobilization of glucose oxidase (GOD)
enzyme on CPE coated by polyaniline (PANI) which was synthesized by cyclic
voltammetry technique. CPE was prepared by mixing 875 mg graphite powder and
375 µl mineral oil and after homogenization, the mixture was packed into the
piston-driven CPE holder with a surface diameter of 4.5 mm [2]. An organic molecule,
2-hydroxy-3-methylcyclohex-2-enone (HMCE) (Fig.1(A)), was added to CPE to modify
glucose biosensor. Also, PANI film was synthesized in two different electrolyte as oxalic
acid and p-toluenesulfonic acid. The first cyclic curves are given in Figure 1(B) and
Figure 1(C) for oxalic acid and p-toluenesulfonic acid, respectively.
Figure 1. The structure of 2-hydroxy-3-methylcyclohex-2-enone (HMCE) (A) and The Cyclic
voltammograms of modified carbon paste electrode (blue) (HMCE-CPE) and unmodified carbon
paste electrode (red) in oxalic acid medium (B) and in p-toluenesulfonic acid medium (C)
As seen in Figure 1 (B) and (C), modified carbon pasta electrode with HMCE showed an
increase in the current for both oxalic acid and p-toluenesulfonic acid mediums when
comparing with unmodified CPE.
References
[1] Stoces, M., Kalcher, K., Svancara, I., Vytras, K., Int.l J Electrochem Sci 6 (2011) 6 1917-1926
[2] Yağız, E., Preparation And Characterization of Carbon Paste Electrode Modified By Different
Ways Using Response Surface Methodology and Use in Biosensor Applications (2015), PhD
Thesis, Mustafa Kemal University.
74
THE USE OF CYCLIC ENONES AS ORGANIC MOLECULES TO
CONSTRUCT OF AMPEROMETRIC GLUCOSE BIOSENSORS
Gul OZYILMAZ, A. Ebru AYDIN, Serbay Bucak, Seda AGCAM, Ali Tuncay OZYILMAZ
Mustafa Kemal University, Department of Chemistry,31000, Hatay, Turkey
A glucose sensitive amperometric biosensor was constructed by immobilizing glucose
oxidase (GOD) onto Pt electrode coated double layers of conductive polymers.
First layer, polypyrrole (PPy), was synthesized in pyrrole, LiClO4, cyclic enones as
organic molecule (6-hydroxy-2-methoxy-3-methyl-cyclohex-2-enone or 2-hydroxy3-methylcyclohex-2-enone) containing acetonitrile medium by cyclic voltammetry
technique. Then, second layer, polianiline (PANI), was synthesized using aniline and HCl
containing aqueous medium onto PPy coating. GOD was immobilized onto conductive
film layered Pt electrode via chitosan and glutaraldehyde. Organic molecules used in
study and electrode scheme was given in Figure 1. α-Hydroxy and α’-hydoxy-αmethoxy cyclic enones were synthesized according to literature procedures [1].
Figure 1. Organic molecules used in PPy layer and schematic representation of obtained electrode.
GOD catalyzes the oxidation of glucose in presence of molecular oxygen by forming
gluconic acid and H2O2 [2]. The current value which was measured by oxidation of
formed H2O2 was proportional by glucose concentration. (Fig.2).
Figure 2. Principle of the amperometric glucose biosensor
References
[1] Demir, A.S., Caliskan, Z., Aydin A.E., Bicer, I., Tetrahedron-Asymmetry 17 (2006) 786-791.
[2] Ozyilmaz, G., Ozyilmaz, A.T., Can F., Applied Biochemistry and Microbiology 47 (2011) 196205.
75
IMPROVEMENT OF GLUCOSE BIOSENSOR BY CATALYTIC
EFFICIENCY OF ZnFe2O4 NANOPARTICLES
Ali Tuncay OZYILMAZ, Esiye İrem BAYRAM and Gul OZYILMAZ
Mustafa Kemal University, Department of Chemistry,31000, Hatay
ZnFe2O4 nanoparticle was used to improve the glucose sensitivity of glucose oxidase
(GOD) electrode. GOD electrode was constructed using three steps. Poly(o-anisidine)
(POA) was synthesized onto Pt electrode by using cyclic voltammogram technique in
sodium oxalate electrolyte at first. Secondly, GOD was immobilized on POA surface with
chitosan and ZnFe2O4 nanoparticles. Finally, surface was reacted with glutaraldehyde
solution. GOD electrode was used in glucose solution by chronoamperometric
technique to obtain current value proportioned with glucose concentration (Figure 1).
Figure 1. Enzymatic reaction occurred on GOD electrode
Imax values of nanoparticle-free and ZnFe2O4 nanoparticle containing GOD electrode
were 6.02 and 11.95 µA, respectively. There were similar results in the literature [1,2]. It
was observed that residual activities at the end of the 20 repeated uses of nanoparticlefree and ZnFe2O4 nanoparticle containing GOD electrodes were 92 % and 93 %,
respectively.
Acknowledgement
The authors wish to thank the Mustafa Kemal University department of Scientific Research Projects
for supporting the this study (Project no:8681)
References
[1] Ren, J., Shi, W., Li, K., Ma, Z., Sensors and Actuators B, 163 (2012) 115-120.
[2] Luo, X., Xu, J., Du, Y., Chen, H., Analytical Biochemistry, 334 (2004) 284-289.
76
GLUCOSE OXİDASE IMMOBILIZATION ON POLY(o-TOLUIDINE)
COATED Pt ELECTRODE FOR AMPEROMETRIC BIOSENSOR
Ali Tuncay OZYILMAZ, Esiye İrem BAYRAM and Gul OZYILMAZ
Mustafa Kemal University, Department of Chemistry,31000, Hatay
A glucose sensitive amperometric biosensor was developed by immobilizing glucose
oxidase (GOD) enzyme on poly(o-toluidine) (POT) coated Pt electrode. Firstly, POT
synthesis was carried out in sodium oxalate (NaOx) medium using cyclic voltammetry
technique on the Pt electrode surface and doped with HCl solution. Then, A thin layer
was constructed by dipping polymer coated electrode in GOD enzyme and ZnFe2O4
nanoparticle containing chitosan solution. Finally immobilization of enzyme on the
surface was carried out via crosslinking by reacting with glutaraldehyde (GAL) solution
(Figure 1).
Figure 1. Schematic representation of enzyme electrode construction.
The current value which was measured by oxidation of forming H2O2 which was
produced enzymatic catalysis. Optimal electrode construction parameters were
determined for segment number, scan rate, monomer, chitosan, glutaraldehyde,
GOD and nanoparticle concentrations. It was observed that, current values measured
for nanoparticle containing electrodes were higher than those of non-containing
counterparts. This result is supported by the literature [1,2]. It was concluded that,
ZnFe2O4 nanoparticles showed catalytic activity on H2O2 decomposition.
Acknowledgement
The authors wish to thank the Mustafa Kemal University department of Scientific Research Projects
References
[1] Ren, J., Shi, W., Li, K., Ma, Z., Sensors and Actuators B, 163 (2012) 115-120.
[2] Luo, X., Xu, J., Du, Y., Chen, H., Analytical Biochemistry, 334 (2004) 284-289.
77
Double Catalytic Centers: Potential Therepautic Applications for
the Treatment of Oxidative Stress
Ferhan Tümer, Songül Şahin, Mehmet Tümer, Muhammet Köse
Chemistry Department, Kahramanmaraş Sütçü Imam University, 46100, Turkey
Porphyrins in natural systems play an important role in biological systems such as in
oxygen transportation (hemoglobin), photosynthesis (chlorophyll) and enzymatic
catalysis (Cytochrome) [1]. The main advantage of utilizing porphyrins as catalysts is
to control of modification of the structures and ease of following structure-catalytic
activity correlation. Catalytic activity is thought to link to the substitute groups on
p-phenyl positions [2] as well as central metal atoms. Schiff bases are considered as an
important class of biological model compounds and their metal complexes are in use
as biomimetic catalysts. Counts all these advantages make the important of the Schiff
bases in bioinorganic chemistry, catalyst, encapsulation, transportation, seperation and
magnetochemistry [3]. These knowledge about porphyrins and Schiff base compounds
have led us to combine these two different class into a new class “Porp-Schiff” type
compound for possible treatment of oxidative stress caused by mainly superoxide.
A new porphyrin- Schiff base ligands and their transition metal complexes were
synthesised and characterised by spectroscopic and analytical methods. The catalytic
performance of the for the dismutation of superoxide (Figure 1) were then evaluated
and their potential usage as metolo-drugs were invetigated.
Figure 1: Dismutation of superoxide by Porphyrin based metal complexes.
Acknowledgments
We are grateful to The Scientific & Technological Research Council of Turkey (TUBITAK) (Project
number: 113Z907) for the support of this research.
References
[1] S. Aronoff, J. Phys. Chem. 62 (1958) 428–431.
[2] G. De Luca, A. Romeo, L.M. Scolaro, G. Ricciardi, A. Rosa, Inorg. Chem. 46 (2007)
5979–5988.
[3] A.J. Atkins, D. Black, A.J. Blake, A. Marin-Bocerra, S. Parsons, L. Ramirez, , M. Schroder. Chem.
Commun. (1996) 457-458.
78
RESPONSE SURFACE METHODOLOGY FOR OPTIMIZATION OF
CONSTRUCTION OF AMPEROMETRIC GLUCOSE BIOSENSORS
Gul OZYILMAZ, Seda AGCAM and Ali Tuncay OZYILMAZ
Mustafa Kemal University, Department of Chemistry, 31040, Hatay
Pt electrode was coated by poly(N-methylpyrrole) (PNMP) by cyclic voltammetry
technique in 10 mM monomer (N-methyl pyrrole) containing sodium oxalate
solution. Glucose sensitive electrode was constituted by immersing PNMP coated Pt
electrode into Glucose Oxidase (GOD) containing chitosan (Chi) solution and then
glutaraldehyde (GAL) solution, respectively. The optimization of concentrations of
Chi (0.25-1.00 mM), GOD (1-4 mg/ml) and GAL (0.025-0.10%) were carried out by
Response Surface Methodology (RSM) using Box-Behnken design. Current values
were measured in presence of glucose and results were evaluated by State Ease Design
Expert 8.0.7.1 software programme (Serial No: 0021-6578) to get ANOVA analysis, 3D
surface, contour and predicted-actual values graphics. The changing of current values by
investigated parameters in presence of glucose were given in Figure 1 (a-b-c-d) as 3D
surface graphics and predicted values vs actual values.
Figure 1. Current values in presence of glucose depending on investigated parameters
(a, b and c), and predicted vs actual value (d)
Acknowledgement
The authors wish to thank the TUBITAK (Project no: 113Z424) and Mustafa Kemal University
department of Scientific Research Projects for supporting the this study (Project no:13781)
79
THE CO-IMMOBILIZED ENZYME SYSTEM FOR LACTOSE SENSITIVE
BIOSENSOR
Esra YAĞIZ, Gul OZYILMAZ and Ali Tuncay OZYILMAZ
Mustafa Kemal University,Department of Chemistry,31000, Hatay
A new lactose sensitive amperometric biosensor was developed using β-galactosidase
(β-GAL) and glucose oxidase (GOx). β-GAL catalyzes the hydrolysis of lactose into
galactose and glucose; afterwards GOx catalyzes the oxidation of glucose by forming
gluconic acid and H2O2 (Ferreira et al., 2004). The current value which was measured
by oxidation of forming H2O2 was proportional by glucose thereby by lactose
concentration. In this study, polyaniline (PANI) was synthesized by two sequential step
onto CPE and modified CPE with 1-(2-cyanoethy)pyrole (CNEP) (Fig 1 a, a'). Biosensor
was constructed by co-immobilization of β-GAL and GOx via glutaraldehyde onto
PANI.
Figure 1. PANI synthesis curves obtained from first (a) and second (a') step; impedance analsis for
CPE/PANI/GOx+β-GAL in buffer (--) and in lactose (-) (b); and for CPE-CNEP/PANI/GOx+β-GAL in
buffer (-) and lactose (-) solution (b')
As seen in Fig. 2 (b) and (b’), charge transfer resistance values which corresponding to
first loop observed at high frequencies were lower in presence of lactose. This means
that biosensor is sensitive to lactose. Besides, charge transfer resistance of modified CPE
were significantly low than that of unmodified CPE. This was concluded by increasing
electron transfer rate in terms of CNEP molecule. Also, KM and IMAX values were obtained
for CPE/PANI/GOD+β-GAL as 1.9 mM and 2.7 µA, respectively; and for CPE-CNEP/
PANI/GOD+β-GAL as 1.23 mM and 4.6 µA, respectively.
Acknowledgement
The authors wish to thank the Mustafa Kemal University Department of Scientific Research Projects
References
[1] Ferreira, L., S., Trierweiler, J. O., De Souza Jr, M. B., Folly, R. O. M., Brazilian Journal of
Chemical Engineering, 21 (2004).
80
CARBON PASTE ELECTRODE BASED SUCROSE BIOSENSOR
Esra YAĞIZ, Gul OZYILMAZ, and Ali Tuncay OZYILMAZ
Recently, carbon paste electrodes (CPE) have been used extensively due to having
many advantages such as low cost, easily preparation and modification [1,2]. A coimmobilized enzyme system based biosensor for sucrose was constructed using CPE
modified by 1-(2-cyanoethyl) pyrrole (CNEP). CPE was prepared by graphite:mineral
oil:CNEP at 1.75:0.38:0.25 weight ratio. Polyaniline (PANI) was synthezed onto modified
CPE by cyclic voltammetry technique in aniline monomer containing sodium oxalate
medium. Invertase and glucose oxidase were immobilized onto PANI film by crosslinking
via glutaraldehyde to obtained sucrose biosensor.
The effect of CNEP was investigated by cyclic voltammograms obtained in buffer
and glucose containing buffer solution (Fig.1-a). As seen in Fig 1-a, current values for
modified electrode were significantly higher than those of unmodified counterpart.
Also for both electrodes, it was clearly seen that, current values were higher in sucrose
containing buffer solution. Similarly, as seen in Fig.1-b, current values depending on
sucrose concentration for modified electrodes were at least three times higher than
those of unmodified electrode.
Figure 1. Cyclic voltammogram of unmodified CPE in buffer (-) and in sucrose (-) solution and cyclic
voltammogram of modified CPE in buffer (--) and sucrose (-) solutions (a); Current values depending
on sucrose concentration, (¢):modified and (£): unmodified CPE (b)
KM and IMAX values for unmodified electrodes were 1.86 mM and 0.98 µA, respectively
and 0.65 mM and 2.7 µA for modified electrodes, respectively.
Acknowledgement
The authors wish to thank the Mustafa Kemal University Department of Scientific Research Projects
References
[1]Boujita, M. Boitard M., El Murr N., Biosensorsand Bioelectronics, 14 (1999) 545-553.
[2]Comba, F. N., Rubianes, M. D., Herrasti, P., Rivas, G. A., Sensors and Actuators B:Chemical. 149
(2010) 306–309.
81
GLUCONIC ACID PRODUCTION BY co-IMMOBILIZED GLUCOSE
OXIDASE-CATALASE ENZYME SYSTEM
Gul OZYILMAZ
Mustafa Kemal University, Department of Chemistry 31040, Hatay
Glucose oxidase (GOD) catalyzes the oxidation of glucose in presence of O2 by
producing gluconic acid and H2O2, while, catalase (CAT) decomposes H2O2 to H2O
and O2 [1]. In this study, GOD and CAT enzymes were co-immobilized in calcium
alginate gel (Ca-ALG) by dripping sodium alginate (Na-Alg) and enzyme mixture into
CaCl2 solution at 4 °C. Co-immobilization parameters were optimized and results were
given in Table 1.
Table 1. Optimization of co-immobilization parameters
Co-immobilized GOD-CAT enzyme system was used to produce gluconic acid from
glucose in batch reactor, recycled packed bed column reactor and continuous column
reactor
Figure 1. Recycled packed bed column reactor (A) and continuous column reactor (B) which were
used to gluconic acid production.
The effect of glucose concentration, flow rate and reaction time on gluconic acid yield
was investigated in detail.
Acknowledgement
The author wish to thank the TUBITAK for supporting the this study (Project no:105T514)
References
[1] Ozyilmaz G., Tukel S.S., Journal of Microbiology and Biotechnology, 17(6) (2007): 960-967
82
N,O-type Schiff base ligands and transition metal complexes
containing functional groups: Structural Characterization and
SOD Activity Studies
İlyas GÖNÜLa, Muhammet KÖSEb, Selahattin SERİNa
Department of Chemistry, Arts and Science Faculty, Cukurova University, 01330, Adana, Turkey
b
Department of Chemistry, Kahramanmaraş Sütçüimam University, K. Maras 46100, Turkey
a
Azomethine group (–C=N–) containing compounds typically known as Schiff bases
have been synthesized by the condensation of primary amines with active carbonyls
[1]. Schiff base metal complexes are among the most explored types of compounds in
coordination chemistry and play an important role in catalysis (including enantioselective
synthesis), materials science, and biochemistry [2]. Oxidative stress results from an
imbalance between the generation of reactive oxygen and nitrogen species (RONS)
and antioxidant defense mechanisms. A great deal of interest has been shown in the
development of therapeutic SOD mimetics for the detoxification of RONS in conditions
associated with oxidative stress [3]. In this study, transition metal complexes of Co(II),
Ni(II) and Cu(II) of 2,4-dimethoxy-N-(2-hydroxy-3-methoxy benzylidene)benzenamine
(HL1) and 2,4-dimethoxy-N-(2-hydroxynaphthalidene) benzenamine (HL2) derived
N,O-type Schiff base ligands were prepared and characterised by FT-IR, 1H,13C-NMR,
TG/DTA, elemental analysis and X-ray diffraction techniques. Additionally, catalytic
activity for the dismutation of superoxide into dioxygen and hydrogen peroxide by the
Schiff base metal complexes were evaluated by a modified indirect chemical method.
References
[1] Pradhan, A., Kumar, A., Chemical and Process Engineering Research, Vol.35, 2015.
[2] Aleksanyan, D. V., Nelyubina, Y. V., Dmitrienko, A.O., Bushmarinov, I. S., Klemenkova, Z. S.,
and Kozlov, V. A. Polyhedron 85:295–301, 2015.
[3] A.E.O. Fisher, D.P. Naughton / Biomedicine & Pharmacotherapy 59, 158–162, 2005.
83
Catalytic Conversion of Superoxide by Porphyrine Based Metal
Complexes
Muhammet Köse, Ferhan Tümer, Mehmet Tümer
Superoxide is a free radical and believed as a contributing cause of many neurological
disorders such as Parkinson`s and Alzheimer`s diseases [1]. Moreover, some types
of cancer are thought to be associated with superoxide. Healthy cells can defense
themselves against ROS damage through the use of superoxide dismutases enzymes
(SODs) which control the level of superoxide at low levels [2]. Natural SOD enzymes
have shown promising therapeutic properties yet suffer as drug candidates due to
some drawbacks. Considerable efforts have been made to obtain stable, non-toxic,
and inexpensive low molecular weight biomimetic molecules which are capable of
catalyzing superoxide dismutation and therefore to provide important therapeutic
applications. Mn(III)porphyrinato complexes also have been found to possess SODlike activity based on indirect analysis [3]. In this project, new porphyrin based Schiff
base ligands and their transition metal complexes were prepared and characterised by
spectroscopic and analytical methods (Figure 1). The catalytic conversion of superoxide
into hydrogen peroxide and molecular oxygen was investigated by an indirect method.
Figure 1: Proposed structures of the complexes used in the catalytic conversion of
superoxide.
Acknowledgments
References
[1] A. Bruce, B. Malfroy and M. Baudry, Proc. Natl. Acad. Sci. U. S. A., 93 (1996) 2312-2316.
[2] J. S. Valentine, in Biological Inorganic Chemistry Structure and Reactivity, Eds. I. Bertini, H. B.
Gray, E. I. Stiefel and J. S. Valentine, University Science Books, California, (2007) 319-353.
[3] R. F. Pasternack, A. Banth, J. M. Pasternack and C. S. Johnson, J. Inorg. Biochem., 15 (1981)
261-267.
84
Porphyrine Based Mn(III) and Fe(III) Complexes as SOD
Mimetics: Subsituent Effects on Catalytic Activity
Mehmet Tümer, Ferhan Tümer, Muhammet Köse
The oxidant and reductant properties of superoxide can be converted to other dangerous
reactive species including hydrogen peroxide, hydroxyl radicals, hypochloride ions and
peroxynitriles which are all harmfull for mamalian cells [1]. Oxidative stress is mainly
due to the overproduction of these reactive oxygen species (ROS) [2]. A biochemical
defence system via enzymes such as superoxide dismutase and catalase is then required
to control the level of superoxide and reactive oxygen species in the living cells. Many
synthetic transition metal complexes have been prepared, displaying a superoxide
scavenger activity and proposed as SOD models for therapeutic applications. Metal
complexes of Cu, Mn, Fe and Ni have been found to disproportionate the superoxide to
molecular oxygen and hydrogen peroxide. Among these, manganese complexes have
received special attention due to lower toxicity of manganese ions [3]. In this study,
porphyrin-Schiff base ligands and their Mn(III) and Fe(III) complexes were prepared
(Figure 1) and the subsituent effect on the catalytic performance for superoxide
scavenging were examined in detail.
Figure 1: Proposed structures of the complexes.
Acknowledgements
References
[1] I. Fridovich, J. Biol. Chem. 264 (1989) 7761-7764.
[2] R. H. Weiss, D. P. Riley, Drugs of the Future, 21 (1996) 383-389.
[3] D. Riley, Chem. Rev. 99 (1999) 2573-2587.
85
Hydrolysis of microalgae oil Chlorella protothecoides via
biocatalysis
Togayhan Kutluka,b, Nurcan Kapucua,b
a
Department of Chemical Engineering, Kocaeli University, 41380 Kocaeli, Turkey
b
Alternative Fuels R&D Center, Kocaeli University, 41040 Kocaeli, Turkey
The hydrolysis of oils and fats is a significant industrial operation: world wide 1.6 × 106
tons of fatty acids are produced every year. The fatty acids synthesised by the hydrolysis
of natural oils and fats from naturally produced renewable raw materials. These products
include oils from corn, rapeseed, sunflower, palm, coconut, olives and rice bran, and
a wide range of animal fats such as cattle and sheep. A large number of high-value
products need fatty acids in their manufactures. These include coatings, adhesives,
specially lubricating oils, shampoos and other cosmetic products [1]. In recent years
microalgae oils are able to replace with traditional raw materials. Microalgaes appear
to be the promising source of fatty acids that their competitive advantages such as oil
contents can climb over 80% by weight of dry biomass and needs to be small harvesting
areas than oil seeds [2]. There are three main processes existing used for the hydrolysis of
fats and oils; high pressure steam splitting, alkaline hydrolysis and enzymatic hydrolysis.
The high temperature and pressure (typically 250°C, 70 bar) necessary for steam splitting
make this process inconvenient for splitting sensitive free fatty acids,this may expose
thermal degradation, and occurs polyunsaturated oils with high iodine number called
polymerize. At the same time alkaline hydrolysis has strains such as an high energy
costs and the need to acidify the soaps formed, to produce the fatty acid products.
Enzymatic hydrolysis of oils may be executes at soft processes conditions (typically 35°C
and atmospheric pressure), making it energy efficient and more environmentally in
contrast to the steam splitting and alkaline process [3]. Therefore in this study we were
investigated that biocatalyst ( Lipozyme TL IM) loading and oil:water mass ratio effect on
hydroysis of microalgae oil. Reactions were implement that 100 ml flasks with oil:water
mass ratio of 1:20 at 50°C 600 rpm 24 hours and different biocatalyst amount. Fatty
acids analyses was performed that NaOH titration according to the ASTM-D5555-95
standard. As a result of experimental studies, maximum fatty acids content of 99% was
reached with 100 mg biocatalyst. This study clearly shows microalge oils are useful as
a raw material for production of fatty acids with environmentally friendly enzymatic
processes rather than alkaline catalysts.
Acknowledgement
We wish to thank Novo Nordisk and Soley Instute for presenting Lipozyme TL 100L and microalgae
oil from Chlorella protothecoides.
86
References
1. Murfy V. R., Bhaf J. , Muniswanas P. K. A. , Hydrolysis Of Oils By Using Immobilized Lipase
Enzyme : A Review, Biotechnology Bioprocess Engineering, 7, 2002, 57-66.
2. Melis A., Green alga hydrogen production: progress, challenges and prospects. International
Journal of Hydrogen Energy 27, 2002, 1217–28,
3. Pronk, W., P. J. A. Kerkhof, C. van Helden, and K. Van’t Reit The hydrolysis of triglycerides by
immobilized lipase in a hydrophilic membrane reactor. Biotechnology and Bioengineering. 32,
1988, 512-518.
87
Immobilization and characterization of Candida rugosa lipase on
magnetic nanoparticles through different spacer arms
Muge SENGULa, Leman BEYKAN*a, Deniz YILDIRIMb, Guzide YUCEBILGICa
University of Cukurova, Faculty of Science and Letters, Department of Chemistry, 01330 Adana,
TURKEY
b
University of Cukurova, Vocational School of Ceyhan, Adana, TURKEY
a
In recent years, much attention has been paid toward synthesis of magnetic nanosized particles and their use for immobilization of enzyme [1,2]. In this study, magnetic
nano-sized Fe3O4 particles were synthesized and characterized by using FT-IR, SEM
and XRD techniques. The size of prepared nanoparticles was found as 158.2 nm. The
magnetic nanoparticles were functionalized with glutaraldehyde and epichlorohydrin
to covalently immobilize Candida rugosa lipase. The optimum pH and temperature
were determined as 7.0 and 40 °C, respectively for all the lipase preparation. The Km, Vmax,
kcat and kcat/Km values were determined as 0.48 mM, 420.7 U/mg protein, 2.82x104 min-1,
58.8x103 min-1 mM-1, respectively for the free lipase. The corresponding values were 1.3
mM, 33.6 U/mg protein, 2.25x103 min-1, 1.73x103 min-1mM-1 for the lipase immobilized
on Fe3O4 through glutaraldehyde spacer arm. For the lipase immobilized on Fe3O4
through epichlorohydrin spacer arm, these values were found as 9.4 mM, 51.7 U/mg
protein, 3.47x103 min-1, 0.37x103 min-1 mM-1. After 20 reuses, the residual activities were
found as 71 and 63% of their initial activities, respectively for the lipases immobilized on
Fe3O4 through glutaraldehyde and epichlorohydrin spacer arms.
References
[1] A.K. Johnson, A.M. Zawadzka, L.A. Deobald, R.L. Crawford, A.J. Paszczynski, Journal of
Nanoparticle Research, 10 (2008) 1009–1025.
[2] M.Cao, Z.Li, J.Wang, W.Ge, T.Yue, R.Li, V.L. Colvin, W.W. Yu, Trends in Food Science and
Technology, 27 (2012) 47–56.
88
Effect of Calcination Temperature on Production of DMN’s over Y
Zeolite Catalyst
Aysel Niftaliyevaa, Ali Karadumanb
ª Selçuk University Faculty of Engineering, Dept. of Chemical Eng. 42075 Konya, TÜRKİYE
Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE
b
Polyethylene naphthalate (PEN) is a relatively new family between polyesters that is
getting a lot of attention currently [1]. PEN shows better properties than polyethylene
terephthalate (PET) such as lower oxygen permeability, thermal shrinkage, youngs
modulus, glass transition temperature, oligomer extraction and higher resistance to
radiation, etc [2-3]. 2,6-dimethylnaphthalene is an important compound for producing
2,6-naphthalene dicarboxylic acid (2,6-NDA), which is significant monomer of the
polyethylene naphthalate (PEN) [4]. One of the 2,6-DMN production method is the
methylation of 2-methylnaphthalene (2-MN) which is the most preferred method.
There are lots of works in the literature related to production of 2,6-DMN [5]. In this
study, the effect of calcination temperature to the synthesis of dymethylnaphthalenes
over Y zeolite are intended. For this purpose, Y zeolite which were available from Zeolyst
(USA) company and 10% La metals doped Y zeolite and calcined at 550°C and 750°C
temperature and tested in the methylation of 2-MN. For all experiments carried out over
Y zeolite catalysis in a continuous flow fixed-bed reactor and molar ratio of 1:5:5 2-MN,
methanol and mesytylene was fed into the reactor. In reactor the quantity of catalyst
was 2cm3, temperature ranging from 400oC to 500oC and weight hourly space velocity
(WHSV) ranging from 1 to 3 h-1. The liquid products were analyzed using the available
ThermoFinnagan DSQ250 GC-MS. As a result, the effect of calcination temperature
over 2-MN conversion, 2,6-DMN yield, 2,6-DMN selectivity and 2,6-DMN/2,7-DMN
ratio was examined. In the all prepared catalysts, increasing the calcination temperature
was decreased the conversion of 2-MN. But the yield of 2,6-DMN was increased by
the increasing of calcination temperature from 550°C to 750°C. Also, the 2,6-DMN/2,7DMN ratio and the selectivity of 2,6-DMN was increased by increasing the calcination
temperature to 750°C.
Acknowledgements
We are thankful and greatfully appreciate The Scientific and Thechnological Research Council of Turkey
(TÜBİTAK) for the support of this work. (Project No:112M297)
References
[1]. Wenyu, T; Weilan, X; Zuoxiang, Z; Ji, Sh. C. J. Chem. Eng.17, (2009), 72-77.
[2]. J. Park,J.Wang,C.Lee,Park,S.Bull.Korean Chem.Soc.23, (2002),1011-1013.
[3]. L.Zhao,X.Guo,M.Liu,X.Wang,Song,C.C.J.Am.Chem.Eng.18,(2010),742-749.
[4]. J. Park,J.Wang,S.Hong,C.W.Lee, Appl. Cata.,292, (2005), 68-75.
[5]. J.Lijun, F.Yunming, H.Haoquan, Catalysis Com.,7, (2006), 255-259.
89
Methylation of Naphthalene Oil Fraction of Coal Tar with
Methanol on Metal/Bimetal Doped Beta Zeolite Catalysts
Aysun Özen¹, Fatih Güleç¹, Aysel Niftaliyeva2, Ali Karaduman¹
¹Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE
²Selçuk University Faculty of Engineering, Dept. of Chemical Eng. 42075 Konya, TÜRKİY
Coal tar naphthalene oil fraction (CTNOF) is composed of many substances such
as significant naphthalene derivatives which are 1-Methylnaphtalene (1-MN),
2-Methylnaphtalene (2-MN) and Dimethylnaphtalenes (DMNs). Due to methylation
of CTNOF, many reaction products including 2-MN and 2,6-dimethylnaphthalene
(2,6 DMN) can be produced [1,2]. 2-MN and 2,6-DMN are desirable products in
terms of used in synthesis of polyethylene naphthalate (PEN) .When compared with
polyethylene terephthalate (PET), PEN has widespread application area due to improved
features such as gas barrier, high tensile strength, heat resistance etc.[3-5]. In this study
synthesis of 2-MN and 2,6-DMN by methylation of CTNOF over Fe/Beta, Au-Fe/Beta
and Pd-Fe/Beta zeolite catalysts was investigated. Metals were doped on Beta by using
wet impregnation method. The experiments were investigated in a fixed bed reactor
using mixture of CTNOF, methanol (methylation agent) and xylene (solvent) with 1:5:5
mass composition as a feedstock. The reactor temperature and weight hourly space
velocity (WHSV) were ranged from 300°C to 400°C and 1h-1 to 3h-1, respectively. The
reaction products were analyzed with using GC-MS which has 60 meter capiler column.
Conversion of Naphthalene, ratio of 2-MN/1-MN and 2,6-DMN/2,7-DMN, selectivity of
2-MN, 2,6-DMN and DMNs were calculated. The modified catalysts were characterized
by XRF, SEM, FTIR and BET techniques. In conclusion, conversion of Naphthalene
increased with temperature and diminished with whsv. The selectivity of 2,6-DMN and
2-MN was enhanced with using Au and Pd doped Beta zeolite. Generally, ratio of and
2-MN/1-MN was above 5.0, 2,6-DMN/2,7-DMN fluctuated around 1.0.
Acknowledgement
We are thankful and greatfully appreciate Ankara University Scientific Research Projects
(AÜ-BAP) for the support of this work. (Project No: 15B0443009)
References
[1] Azpiroz M.D.G., Balanco, C.G., Banciella M.D.C., Fuel Processing Technology, 89,( 2008), 111-117.
[2] Tang, W., Fang, M., Wang, H., Yu, P., Wang, Q., Luo Z., Chemical Engineering Journal, 236,(
2014),529-537.
[3] Wu,W., Wu,W., Kikhtyanin,O.V., Lingfei,L., Toktarev, A.V., Ayupov,A.B., Khabibulin,J.F.,
Echevsky,G.V., Huang,J., Applied Catalysis A: General, 375, (2010), 279-288.
[4] Niftaliyeva, A., Güleç,F., Şimşek,E,H., Güllü,M., Karaduman,A., Anadolu University Journal of Science
and Technology,16, (2015),167-178.
[5] Zhao,L., Guo,X., Liu,M., Wang,X., Song, C., Chinese Journal of Chemical Engineering 18 ,(2010), 742749.
90
MODIFICATION OF ACTIVATED CARBON BASED ADSORBENTS FOR
CO2 ADSORPTION
Melek Selcen BAŞARa, Burcu SELEN ÇAĞLAYANa,b, Ahmet Erhan AKSOYLUa
a
Boğaziçi University, Department of Chemical Engineering, 34342, Bebek, Istanbul
Boğaziçi University, Advanced Technologies R&D Center, 34342, Bebek, Istanbul
b
Carbon dioxide is the primary greenhouse gas, which is responsible for global warming
and climate change. Main emissions arise from the release as one of the flue gases from
the combustion of fossil fuels such as coal, natural gas, and oil and as a by-product
from industrial processes such as cement, iron, and steel [1]. Adsorption is an attractive
technique in CO2 removal in terms of its cost advantage, low energy requirement,
ease of applicability and regeneration over a relatively wide range of temperatures and
pressures. An ideal adsorbent for effective CO2 capture should possess the following
characteristics; (i) high surface area, (ii) big pore volume, (iii) high selectivity for CO2,
(iv) adequate adsorption/desorption kinetics and (v) stable adsorption capacity and
high mechanical strength after repeated adsorption and desorption cycles. Since
the adsorption performance of a solid sorbent, e.g. activated carbon (AC), depends
on its porous structure and surface chemistry, modification of AC-based adsorbents
through different thermal and chemical pretreatments enhanced effectiveness of ACs
by changing the surface functional groups in capture of CO2 [2,3].
In the present work, the aim is to introduce basic N-containing groups to the carbon
surface through different ammonia treatment methods and to observe the contribution
of the treatment effects on the adsorption properties of modified ACs towards acid
agents like CO2. More specifically, the effect of liquid ammonia (wet-amination),
gaseous ammonia (amination) and ammonia-oxygen (ammoxidation) treatment at
different temperature and flow compositions to produce highly CO2-selective ACbased adsorbents are studied.
References
[1] Shafeeyan, M.S., Daud, W.M.A.W., Houshmand, A., Arami-Niya A., Fuel, 94 (2012) 465-472.
[2] Adelodun, A.A., Lim, Y.-H., Jo, Y.-M., Journal of Analytical and Applied Pyrolysis, 105 (2014)
191-198.
[3] Selen Caglayan, B., Aksoylu, A.E., Journal of Hazardous Materials, 252-253 (2013) 19-28.
91
ENHANCING PHOTOCATALYTIC ACTIVITY OF ZnO NANOROD WITH
HEAT TREATMENT
Fatih TEZCANa, Gülfeza KARDAŞa
Çukurova University, Science and Literature Faculty Chemistry Department, 01330, Adana
a
Enhancing energy demands of human have accelerated the investigation of the
photovoltaic application for photoelectrochemical(PEC) water splitting under solar
light irradiation[1, 2]. Among the semiconductor materials, ZnO has been abundantly
examined as photoanode for PEC water splitting in order to the appropriate band gap
of ZnO can transform water to H2 via photoelectrolysis, low-cost and environmental
friendly. On the other hand, efficiency of ZnO is not adequate for PEC cells. Different
heat treatments have been enhanced photoanode the PEC. For this reason our study,
the electrochemically sensitized ZnO nanorods were calcinated at 350°C. Surface
of ZnO nano material was characterized Scanning Electron Microscopy(SEM).
Photoluminescence (PL) properties were carried out Flurorescence Spectrometer
LS55. PEC measurements were examined in a convenient three-electrodes cell, an
electrochemical analyzer Gamry (interface 1000) and a 300W Xe lamp solar simulator
(100 mW/cm2). The calcinated ZnO nanorod has higher photocurrent density and PL
properties than uncalcinated ZnO nanorod. Therewithal, SEM images of ZnO nanorod
change with deposition potential.
Figure 1. SEM imagine of -0.7 V(a), -0.8 V(b) and -0.9 V(c) ZnO nanorod using electrochemical
deposition method
The authors are greatly thankful to Scientific Research Project of Çukurova University
(Project No: FDK-2014-3488)
References
[1] K.Y. Guo, Z.F. Liu, Y. Wang, Y.F. Zhao, Y.C. Xiao, J.H. Han, Y.J. Li, B. Wang, T. Cui,
International Journal of Hydrogen Energy, 39 (2014) 13408-13414.
[2] C. Wang, Y.J. Feng, L. Cai, X.Y. Yang, J.F. He, W.S. Yan, Q.H. Liu, Z.H. Sun, F.C. Hu, Z. Xie, T.
Yao, S.Q. Wei, Journal of Power Sources, 269 (2014) 24-30.
92
Low Platinum Loading Electrode for Formic Acid Fuel Cell
Prepared by Ion-Beam Assisted Deposition
M. Selim ÇÖGENLİa, Sanjeev MUKERJEEb, Ayşe BAYRAKÇEKEN YURTCANa,c
Nanoscience and Nanoengineering Department, Atatürk University, Erzurum 25240, Turkey
Department of Chemistry and Chemical Biology, Northeastern University, Boston-MA 02115,
USA
c
Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum
25240, Turkey
a
b
Formic acid has a high open cell potential (OCP), and the fact that it is liquid at room
temperature and non-toxic in diluted solutions makes it an attractive fuel candidate [1].
Direct formic acid fuel cells (DFAFCs) are promising alternatives to hydrogen proton
exchange membrane fuel cells (PEMFC) for electronic applications.
Ion-beam assisted deposition (IBAD) is a vacuum-deposition process that combines
physical vapor deposition (PVD) with ion-beam bombardment. Vapor of coating
atoms are generated with an electron-beam evaporator and deposited on a substrate
[2]. In this study, anode electrode is prepared with the IBAD method with 0.08mgPt/
cm2 loading and cathode electrode is prepared with painting method with 4mgPt/cm2
loading. Structural properties of IBAD electrode were determined by using SEM images
and EDS (Figure 1). Prepared electrode by direct coating (via IBAD) of un-catalyzed
carbon cloth, at first will be used at anode electrode side for DFAFCs then will be
compared with other studies in the literature.
Figure1. SEM image and EDS result of ibad electrode
References
[1]Yu X, Pickup P G. J Power Sources. 2008;182:124–132.
[2] M.S. Saha et al. / Electrochimica Acta 51 (2006) 4680–4692.
93
Pt Catalyst Supported on Bi2O3 for Direct Formic Acid Fuel Cells
M. Selim ÇÖGENLİa, Ayşe BAYRAKÇEKEN YURTCANa,b
Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum 25240,
Turkey
a
b
In recent years, formic acid has been used as an important fuel either without reformation
(in direct formic acid fuel cells, DFAFCs). Platinum (Pt) is the most common catalyst in
both anode and cathode fuel cell reactions. When formic acid is used as the fuel, the
catalyst can be poisoned Because of formic acid oxidized by Pt to CO and CO2. This can
cause significant problems for the fuel cells.
Carbon has traditionally been the most common material of choice for fuel cell
electrocatalyst supports. In this study, Bi2O3 was used for support material because
of some advantages. Geng et al. reported that Pt/Bi2O3 catalyst are tolerant to CO
poisoning and have higher electrocatalytic activity for CO oxidation [1]. At another
study, PtRu/Bi2O3 showed high selectivity towards dehydrogenation and the rate of
hydrogen generation is determined [2].
In this study, Bi2O3 supported Pt catalyst was prepared by using microwave irradiation
technique. Firstly, required amounts of Bi2O3 and aqueous solution of H2PtCl6 added in
ethylene glycol and then stirred for 30 min. Then the resulting mixture was reduced
in microwave oven. The structural properties of the Bi2O3 and Pt/Bi2O3 catalyst were
characterized by SEM (Figure 1). Other physicochemical characterizations will also
be made. Electrocatalytic activity of Pt/Bi2O3 catalyst for formic acid oxidation will be
tested with CV measurements.
Figure 1. SEM images of a) Bi2O3 b) Pt/Bi2O3
References
[1] J. Geng et al. Catal Lett (2010) 135:114–119
[2] Tsang Kwok-ying, HKU Theses Online, The University of Hong Kong, 2007.
94
CATALYTIC GASIFICATION OF ÇAN LIGNITE
Açelya Seçer Ateş, Arif Hasanoğlu
Çukurova University,Chemistry Department, Adana
The majority of the world’s energy requirement is provided by fossil fuels. The direct
burning of fossil fuels causes serious environmental problems by effecting atmosphere,
water sources etc. The current reserves of the fossil fuels ,production coasts, usage
amounts and the extrapolation of the these statistics to future indicates that, the fossil
fuels will be major for providing worlds energy requirements in the future. Furthermore,
coal, probably, will be the most dominant energy source in the first half of 22th century.
Therefore, research on coal and coal derivatives are getting more important for
improving the alternative usage of coal, such as production of hydrogen from coal.
Catalytic hydrogen production from coal is an important way to produce high yiled
hydrogen gas from coal. Steam is used as gasification agent in traditional methods of
production of hydrogen from coal and the process temperatures are over 1000 °C. Also,
A steam generator is used to produce steam, and carrier gases are used in these traditional
methods. In this study, a new method, which will be called as atmospheric pressure
vapor phase reforming (AVPR), in which water is directly vaporized in the gasification
reactor instead of producing steam with steam generator, is used to produce hydrogen
from coal. For this aim, Çan lignite, a Turkish coal with a % 4,6 S content, is gasificated
for hydrogen production with AVPR method by using different catalysts. Coal samples
including catalysts were prepared with Na2CO3,K2CO3,CdSO4,FeSO4,FeCl3,CaNO3, NiCl2
salts by impregnation. Gasification experiments were performed at , 700°C with a
0,5ml/min flow rate. Maximum gasification volume and hydrogen yield were obtained
with Na2CO3 catalyst with a volume of 1053,5 ±30,4 ml/h and %74,7±1,0 H2.
References:
[1] Yeboah,D.Y., Xu, H., Sheth,A., Agrawal,P., Catalytic Gasification of Coal using Eutectic Salt
Mixtures , 2001.
95
Ceria Incorporated Alumina Supported Nickel Catalysts for
Steam Reforming Reaction of Diesel Fuel
Arzu Arslana, Arife Derya Deniz Kaynarb, Naime Aslı Sezgia, Timur Doğua
a
Middle East Technical University, 06800, Ankara, Turkey
b
Vestel Defense Industry, 06800, Ankara, Turkey
Increase in energy demand with developing technology introduces a need for synthesis
of alternative fuels. Hydrogen is considered as the energy carrier of the future in fuel-cell
applications. Hydrogen production from diesel through steam reforming reaction (DSR)
is an attractive route, due to its easy accessibility and very high hydrogen content (7080% in volume base) [1]. Alumina supported nickel catalysts are generally used in steam
reforming of hydrocarbons due to their high catalytic activity, availability and low cost.
However, they are also active towards side reactions and carbon deposition. An ideal
catalyst support should possess a strong interaction with nickel clusters, strong oxygen
storage-release capacity, such as CeO2. In this study, effect of catalyst support structure
and composition on its catalytic performance in DSR was investigated. Alumina was
synthesized by following the evaporation-induced-self-assembly method (Al2O3-EISA)
[2]. Procedure was modified to synthesize ceria-alumina with a ceria incorporation
amount of 20 wt.% (CeO2-Al2O3-EISA). In order to analyze the effect of synthesis
method, commercial Al2O3 (Al2O3-COM) and 20 wt.% ceria impregnated commercial
alumina (CeO2@Al2O3-COM) were also characterized and tested in DSR. According
to N2 physisorption analysis, BET surface areas of Al2O3-EISA Al2O3-COM CeO2-Al2O3EISA, and CeO2@Al2O3-COM materials were found to be 265, 190, 81, and 168 m2/g,
respectively. It can be deduced that ceria addition to the synthesis solution significantly
altered the mesoporous structure. However, impregnation of ceria on commercial
alumina reduced surface area and pore volume of the material by plugging the pores.
Activity test results showed that ceria incorporation enhanced hydrogen production
by minimizing side product formation. Results proved that CeO2-Al2O3 material was a
promising candidate as a catalyst support for steam reforming applications.
Acknowledgement
Financial supports of Tübitak through project number 213M027, Vestel Defence Industry and
İbrahim Pamuk are gratefully acknowledged.
References
[1] A. D. Deniz, D. Dogu, and N. Yasyerli, Fuel Process. Technol., 140 (2015.), 96–103.
[2] S. Gunduz and T. Dogu, Ind Eng Chem, 51, 26 (2012), 8796–8805.
96
PtCu/C BIMETALLIC CATALYSTS FOR PEM FUEL CELLS
Ayşenur ÖZTÜRKa, Elif DAŞb, Gamze BOZKURTa,b, Ayşe BAYRAKÇEKEN YURTCANa,b
a
b
PEM fuel cell is a good alternative as power generator and Pt based catalysts are the
most common materials to improve sluggish oxygen reduction reaction (ORR) rate
in these systems. However, it is confronted with two major problems regarding Pt
catalysts. One of them is using hydrogen gas that contains CO as reactant in fuel cell,
leads to Pt metal poisoning because strongly adsorption of CO on Pt. The other one
is expensiveness and inability of Pt metal. Novel cheaper catalysts that are comparable
with Pt attract great attention. Therefore, Pt-containing binary and ternary alloys have
been investigated in literature as catalyst in PEM fuel cell.
Synergy of platinum and other transition metals in alloy form provides higher catalytic
activity for the ORR than pure platinum catalyst [1]. This improvement can be
attributed to modified binding of surface reaction intermediates and delicate catalytic
reactivity control over the metal surface. The studies that are relevant to Pt-Pd, Pt-Ni,
Pt-Co binary catalysts have been mostly encountered over the past decade [2].
In the scope of this study, Cu was used as transition metal that is less prevalent in literature
and PtCu bimetallic catalyst on carbon support was prepared by microwave-irradiation
technique. This method includes reduction step in order to dope metal particles on
the support material. Additionally in an attempt to facilitate liquid water transport in
catalyst layer, hydrophobic polymer was included in catalyst ink with different loadings
[3]. Polydimethylsiloxane (PDMS) polymer was preferred for this purpose due to its high
hydrophobic property and chemical stability [4]. Physicochemical and electrochemical
characterizations of prepared catalysts were performed.
References
[1] A. Seo, J. Lee, K. Han, H. Kim, Electrochimica Acta, 52 (2006) 1603-1611.
[2] P. Mani, R. Srivastava, P. Strasser, The Journal of Physical Chemistry, 112 (2008) 2770-2778.
[3] G. S. Avcıoğlu, B. Fıçıcılar, A. Bayrakçeken, İ. Eroğlu, International Journal of Hydrogen Energy,
40 (2015) 7720-7731 .
[4] Q. Ke, W. Fu, H. Jin, L. Zhang, T. Tang, J. Zhang, Surface & Coatings Technology, 205 (2011)
4910-4914.
97
Effects of Synthesis Route and Calcination Temperature on
Structural and Acidic Properties of Mesoporous -Al2O3
D. Erkal1, B. Pekmezci1, N. Oktar1, G. Doğu1, N.A. Sezgi2, T. Doğu2
GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey;
Middle East Technical University, Department of Chemical Engineering, Ankara, Turkey.
1
2
Due to their high surface area and low diffusion resistance, mesoporous materials with
ordered pore structures have been considered as potential catalyst support materials
[1]. Among these materials, mesoporous alumina has attracted great interest because of
its high thermal stability and its acidic properties. These materials have tunable pore size
between 2-10 nm, large surface area, narrow pore-size distribution and moderate Lewis
acidity [2]. In this study, effects of synthesis procedure and the calcination temperature
on the structure of mesoporous alumina were examined. Hydrothermal and sol-jel
processes have been followed as synthesis routes and these materials were calcinated at
different temperatures in the range of 750-950 oC. XRD results revealed that, γ-Al2O3
was succesfully formed and crystal size was increased with an increase in calcination
temperature. Nitrogen adsorption/desorption analysis indicated some decrease of BET
surface area of the materials with an increase in temperature. In the case of the material
which was synthesized following the hydrothermal route, the highest surface area (235
m²/g) was obtained at a calcination temperature of 750oC. Surface area of the material
which was synthesized by the sol-gel route was 206.6 m2/g. The average pore diameter
of this material was about 9.8 nm. Surface acidities of these materials were evaluated by
the DRIFTS analysis of pyridine adsorbed samples. Bronsted acidities of these materials
were further increased by incorporation of heteropoly acids into their structure for use
as solid acid catalysts in dehydration of methanol to produce dimethyl ether.
Acknowledgement
Financial support of TUBITAK 115M377 was gratefully acknowledged
Reference
[1] Yuan Q., Yin A.-X., Luo C., Sun L.-D., Zhang Y.-W., Duan W.-T., Liu H.-C., Yan C.-H., Facile
Synthesis for Ordered Mesoporous gamma-Aluminas with High Thermal Stability, Journal of the
American Chemical Society, 130: 3465–3472, 2008.
[2] Márquez-Alvarez C., Žilková N., Pérez-Pariente J., Čejka J., Synthesis, Characterization and
Catalytic Applications of Organized Mesoporous Aluminas, Catalysis Reviews Science and
Engineering, 50: 222–286, 2008.
98
Effect of Marl on the Production of Biodiesel as a Heterogeneous
Catalyst
Bakhtiyar NAJAFOVa, Niyazi Alper TAPANa
a
Gazi Üniversity, Engineering Faculty, Chemical Engineering Department, Maltepe, 06570,
ANKARA
Biodiesel which is alkyl esters of fatty acids, is an alternative to diesel fuel due to its
equivalent engine performance and low emissions to the environment. The aim of
this study is to examine reaction variables such as the effect of marl catalyst ratio,
reaction time and determine optimum conditions for biodiesel production. After
transesterification of domestic waste vegetable oil, product samples were analyzed by
the amount of glycerol produced and viscosity, density, flash point, acidity, refractive
index of biodiesel. The results of this study indicate that optimum conditions for 99.35%
biodiesel yield are 55oC reaction temperature, (6:1) alcohol to oil ratio, 1% NaOH , 1%
marl catalyst by weight and 30 min reaction time.
99
Hydrogen Production over Mesoporous Carbon Supported Iron
Nanocatalysts using Microwave Reactor system
C.Korkusuz1 D.Varışlı1 T.Doğu2
Gazi University, Department of Chemical Engineering, 06570, Ankara Turkey
Middle East Technical University, Department of Chemical Engineering, 06500,Ankara, Turkey.
1
2
Ammonia is an important raw material for hydrogen due to its superior properties suc
as COx free hydrogen, which is necessary for fuel cell applications, can be produced by
its decomposition reaction. Nowadays, alternative heat sources such as microwave has
gained great attention. Higher conversion values can be obtained at a lower reaction
temperature in the microwave assisted system in comparison to the conventional
systems due to the efficient heating of active sites present in the structure of the catalyst
by means of microwave heating [1]. In the literature, it can be seen that alternative
heating systems have been applied to hydrogen production from different sources such
as methane, biomass, however, any studies related with the microwave application to
ammonia decomposition reaction cannot be found.
In this work, Iron (Fe) incorporated Mesoporous Carbon (MC) supported catalysts were
prepared by impregnation procedure and the synthesized catalysts were characterized
with different techniques such as TGA-DTA, TPA, XRD, Nitrogen Physisorption, SEMEDX, HRTEM and they were tested in both Microwave Reactor System and Conventional
Heating system. Results of experiments show that higher conversion values were
achieved at lower reaction temperatures in microwave system. Ammonia conversion
value of 55% was obtained at 350oC and total conversion was achieved at 450oC in
the experiments that were carried out in Microwave Reactor system with GHSVNH3
of 36,000 ml/hgcat while negligible conversion of ammonia was seen in conventional
heating systems at these reaction temperatures. Total conversion could be achieved at
600oC in conventional heating system.
Acknowledgement
Financial support of TUBITAK 214M148 was gratefully acknowledged.
Reference
1- S.Gündüz, T. Dogu, Applied Catalysis B: Applied Catalysis B: Environmental 168-169 (2015)
497–508
2- H. Zhang, Y. Alhamed, Y. Kojima, A.Zahrani, H. Miyaoka, L. Petrov, İnternational Journal of
Hydrogen Energy 39 (2014) 277-287
3-X. Duan, G. Qian,J. Zhou,X. Zhou, Catalysis Today 186 (2012) 48– 53
100
ELECTROCHEMICAL BEHAVIOUR OF HYBRID NANOSTRUCTURED
MATERIALS FOR PEM FUEL CELL ELECTROCATALYSTS
Elif DAŞa, Selmiye ALKAN GÜRSELb, Lale IŞIKEL ŞANLIb, Ayşe BAYRAKÇEKEN YURTCANa,c
Faculty of Engineering & Natural Sciences, Nanotechnology Research & Application Center
(Sunum), Sabancı University, Istanbul 34956, Turkey
c
a
b
Graphene based hybrid materials has recieved enormous attention which seek to
combine the attractive features of the two dimensional lattice with some additional
functionality afforded by a second component such as metal or semiconductor
nanoparticles, polymers or organic molecules [1]. These hybrid structures have shown
promise for use as catalysts and electrodes for fuel cells, supercapacitors and batteries.
In this study, carbon black-graphene (CB-G) hybrid composite support materials are
prepared by mixing CB with G. Pt nanoparticles on hybrid materials are obtained by
using superciritical carbon dioxide deposition (scCO2) technique. A certain amount of
precursor is firstly dissolved in scCO2 (at 35˚C and 12 MPa) and then adsorbed on the
hybrid materials and the catalysts were obtained via thermal conversion of the adsorbed
precursor molecule to Pt metal. Pt loading over the hybrid materials were determined
by using TGA analysis. Electrochemical characterizations of all prepared catalysts are
made. According to polarization curve of the catalysts, the hybrid composite ratio of
50:50 shows the best PEM fuel cell performance as shown in Figure 1.
Figure 1. Polarization curve of electrocatalysts
Acknowledgements
The authors are greatfully acknowledge the financial support of TÜBİTAK with grant numbers of
114F029 and 114F506.
References
[1] Tepeli Y, Anik U. Comparison of performances of bioanodes modified with graphene oxide and
graphene–platinum hybrid nanoparticles. Electrochemistry Communications. 2015;57:31-4
101
CARBON BLACK-GRAPHENE HYBRID SUPPORT MATERIALS FOR
PEM FUEL CELL ELECTROCATALYSTS
Elif DAŞa, Selmiye ALKAN GÜRSELb, Lale IŞIKEL ŞANLIb, Ayşe BAYRAKÇEKEN YURTCANa,c,
Faculty of Engineering & Natural Sciences, Nanotechnology Research & Application Center
(Sunum), Sabancı University, Istanbul 34956, Turkey
c
a
b
Proton exchange membrane fuel cell (PEMFC) technology has recieved significant
attention as a potential alternative source of power generation thanks to high efficiency,
high power density, low operating temperature. However, long-term durability still
needs to be improved. Platinum (Pt) catalysts supported carbon blacks (CB) have been
widely used as electrocatalysts for PEMFCs, but CB can be easily oxidized at the potential
of oxygen reduction reaction [1]. The oxidation of CB can cause agglomeration and
loss of Pt nanoparticles, resulting in a decrease of the electrochemical surface area and
activity of the electrocatalysts. Up to now, many attempts have been made to solve the
durability problem by introducing robust materials as a catalyst support and graphene
(G) also is one of them which exhibits highly ordered graphitic structure.
In present study, we report hybrid material supported Pt catalysts (Pt/CB-G). Firstly,
CB-G hybrid support materials are prepared by mixing CB with G at 50, 60, 70, 80, 90 and
100 wt% percentages of G. Pt nanoparticles over hybrid materials are obtained by using
superciritical carbon dioxide deposition (scCO2) technique which is facile and effective.
1,5-dimethyl platinum cyclooctadien (Me2PtCOD) is used as the Pt organometallic
precursor. A certain amount of precursor is firstly dissolved in scCO2 (at 35˚C and 12
MPa) and then adsorbed on the hybrid materials. The precursor is decomposed to
metallic Pt form with heat treatment at 400˚C for 4 h in nitrogen atmosphere. Surface
areas of the hybrid materials are determined by using BET analysis. All prepared catalysts
are characterized by using TEM and XRD techniques.
Acknowledgements
The authors are greatfully acknowledge the financial support of TÜBİTAK with grant numbers of
114F029 and 114F506.
References
[1] J. Jung, M. Kwon, H.-R. Kim, J. Kim, International Journal of Hydrogen Energy, 39 (2014)
966-973.
102
INFLUENCE OF TYPE OF CARBON SUPPORT ON THE REFORMING
ACTIVITY AND SELECTIVITY OF SUPPORTED Pt CATALYSTS FOR
APR OF GLUCOSE
Burçak Kaya Özsela*, Bahar Meryemoğlub, Mehtap Kurtuluşb, Arif Hasanoğlub, Sibel
Irmakc
Department of Chemistry, Bursa Technical University, 16190 Bursa, TURKEY
b
Department of Chemistry, University of Cukurova, 01330 Adana, TURKEY
c
Biological Systems Engineering, University of Nebraska, Lincoln, NE, 68583-0726, USA
a
In recent years, due to the reduction of fossil fuel resources and increasing emissions
of greenhouse gases, the interest on the production of alternative energy from
renewable and eco-friendly sources such as biomass which is cheap and abundant has
increased considerably. Aqueous Phase Reforming (APR) of real biomass or suitable
model compounds (glycerol, glucose etc.) is an alternative process to convert biomass
material into hydrogen energy and hydrogen thus produced can be used in fuel cells
to generate electricity or can be used as a fuel directly instead of fossil fuels [1-3] .
One of the biggest challenges for hydrogen production by aqueous- phase reforming
of biomass compounds is catalyst development for improving the conversion. In
this study, we aimed to see the influences of different commercial activated carbon
support materials on the activity and selectivity of Aqueous Phase Reforming catalysts.
Activated carbon (Sigma-Aldrich), Elorit, Superdarco and Norit-rox 0.8 (Norit Inc.)
were tested as supportive materials for nano-sized and uniform Pt metal deposition.
Pt was doped as the only active metal to different activated carbon supports so as to
differentiate the reforming performance of various carbon supported Pt catalysts. We
have used wetness impregnation method to load the metal precursor on activated
carbon support, followed by two sequential reduction methods; reduction with NaBH4
solution and termal reduction [4]. The structural characterization of the supported
catalysts were investigated by using X-Ray diffraction and TEM. Surface area and
pore size distribution were measured by N2 adsorption–desorption at 77 K using a
Quantachrome Autosorb-6 Analyzer. The APR experiments are carried out in batch
using a 100 mL Parr micro bench reactor equipped with magnetic drive stirrer heated
to 250 °C for two hours. All gaseous products were analyzed by a dual-channel gas
chromatograph (GC) system equipped with two thermal conductivity detectors. It was
observed that the overall catalytic activities of these reforming catalysts when used in
the APR of glucose for hydrogen production decreased in the following order: Pt-elorit
> Pt-activated carbon > Pt-superdarco > Pt-norit-rox0.8. The results show that the
type of support material has a direct influence on the kinetic behavior and affects the
reforming peformance of catalysts for aqueous phase reforming of glucose solution.
103
Elorit, a steam activated carbon, exhibited better catalytic activity compared to other
activated carbon supports.
References
[1] G.W. Huber, J.W. Shabaker, S.T. Evans, J.A. Dumesic, Applied Catalysis B 62 (2006) 226-35.
[2] B. Kaya, S. Irmak, A. Hesenov, O. Erbatur, Bioresource Technology 37 (2012) 17844-17852.
[3] B. Meryemoglu, S. Irmak, A. Hesenov, O. Erbatur, Int. J. Hydrogen Energy 37 (2012) 1784417852.
[4] B. Meryemoglu, S. Irmak, B. Kaya Ozsel, A. Hasanoglu, O. Erbatur, Int. J. Hydrogen Energy 40
(2015) 14826-14832.
104
CoRh NANOPARTICLES: SYNTHESIS, CHARACTERIZATION, THEIR
USE AS CATALYST IN THE HYDROLYSIS OF HYDRAZINE BORANE
Bayram Abaya, Nihat Tunça, Murat Rakapb,
a
Yuzuncu Yil University, Department of Chemistry, 65080, Van
b
Yuzuncu Yil University, Maritime Faculty, 65080, Van
Lightweight boron containing hydride compounds are very useful hydrogen storage
materials due to their outstanding properties like high stability, high hydrogen content,
safe storage, easy catalytic hydrogen release at room temperature and environmentally
benign side products formation [1]. Among these storage materials, one of the mostly
used materials is hydrazine borane (N2H4BH3, HB). HB has 15.4 wt% of hydrogen and
can easily be synthesized from the reaction of hydrazine hemisulfate and sodium
borohydride in dioxane at room temperature [2]. Hydrazine borane releases 3 moles of
hydrogen gas upon hydrolysis in the presence of appropriate metal catalysts in aqueous
solution.
In this study, PVP-stabilized cobalt-rhodium nanoparticles was synthesized and
characterized by UV-VIS spectroscopy, TEM, XRD, and XPS techniques. Catalytic activity
of CoRh@PVP nanoparticles in the hydrolysis of hydrazine borane was investigated and
related kinetic data were obtained.
References
[1] Eberle, U., Felderhoff, M., Schueth, F. Angew. Chem. Int. Ed. 48 (2009) 6608-6630.
[2] Hannauer, J., Akdim, O., Demirci, U.B., Geantet, C., Herrmann, J.M., Mielec, P., Xu, Q. Energ.
Env. Sci. 4 (2011) 3355–3358.
105
Ni(II) COMPLEX COVERED ZnO FILM OF PHOTOCATALYSTS FOR
EFFICIENT HYDROGEN PRODUCTION
Eylül Büşra HEREYTANİa, Fatih TEZCANa, Bilgehan GÜZELa, Gülfeza KARDAŞa, Osman
SERİNDAĞb
Çukurova University, Faculty of Science and Letters Department of Chemistry, Adana
b
Kanuni University, Institute of Science and Technology, Adana
a
ZnO semiconductor photo electrochemical (PEC) water splitting systems are promised
as a renewable-energy resources using with solarlight [1,2]. The only drawback of ZnO
semiconductor is that it absorbs a small portion of the solar spectrum in the UV region.
Therefore, enhancing to utilize of solar energy is essential to shift absorption of the
visible light region. Dye-sensitized organic molecules are demonstrated to be one of
the possible methods for dealing with this issue[3]. Aminomethlydiphospine Ni(II)
has been synthesized by our group in order to its investigate photoluminescence and
photo catalytic properties to generate H2 from water. Photo electrochemical (PEC)
measurements were carried out in a convenient three-electrodes cell which bare ZnO
and Ni complex film covered ZnO as working electrodes, an Ag/AgCl electrode was
used as the reference electrode and platinum plate was used as the counter electrode
at 0.5 M Na2SO4 as the electrolyte. Photoluminescence (PL) property of the electrode
was investigated with Fluorescence Spectrometer LS 55. When Ni complex film was
covered ZnO surface, the photocurrent density and photoluminescence intensity
enhanced according to bare ZnO.
Figure 1. PL spectra of Aminomethlydiphospine Ni(II) [Ni(dppab)] covered ZnO film
and bare ZnO film
The authors are greatly thankful to Scientific Research Project of Çukurova University
(Project No: FYL-2015-5201)
106
References
[1] C.H. Hsu, D.H. Chen, International Journal of Hydrogen Energy, 36 (2011) 15538-15547.
[2] Y.K. Hsu, S.Y. Fu, M.H. Chen, Y.C. Chen, Y.G. Lin, Electrochimica Acta, 120 (2014) 1-5.
[3] T.A.M. Devens Gust, and Ana L. Moore, Accounts of Chemical Research, 42 (2009) 1890-1898.
107
Pt Catalyst Supported on High Surface Area MCM-41 and its
Catalytic Activity for Formic Acid Oxidation
Niyazi ÖZÇELİKa, M. Selim ÇÖGENLİa, Ayşe BAYRAKÇEKEN YURTCANa,b
Faculty of Engineering, Department of Chemical Engineering, Ataturk University, Erzurum 25240,
Turkey
a
b
Direct formic acid fuel cells (DFAFCs) have been reported as an alternative for green
energy. We report here the comparative studies of high surface area support materials
and their influence on catalytic activities towards the electrochemical oxidation of
formic acid. MCM-41 has been used in various areas including drug delivery, electronic,
column seperation and catalysts because of its high surface area and mesoporous pore
size distribution ranging from 2 nm to 50 nm [1].
MCM-41 with high surface area was prepared by sol-gel method [2]. MCM-41 supported
Pt catalyst was prepared by using microwave irradiation technique. Firstly, required
amounts of MCM-41 and aqueous solution of H2PtCl6 added in ethylene glycol and
then stirred for 30 min. Then the resulting mixture was reduced in microwave oven.
MCM-41 had a BET surface area of 1057 m2/g this value is significantly higher than
Vulcan carbon (250 m2/g). The characteristic peaks for fcc Pt is clearly seen from XRD
(Figure 1). In this study, MCM-41 and carbon supported Pt catalysts will be tested for
formic acid oxidation by CV measurements.
Figure 1: XRD result of MCM-41 supported Pt catalyst
References
[1] Taguchi A. and Schüth F. Microporous and mesoporous materials 77 (2005) 1-45
[2] Hu et al. Microporous and mesoporous materials 147 (2012) 94-101
108
Development of Co-B/ Sepiolite Catalysts for Hydrogen
Generation by Hydrolysis of Sodium Borohydride
Seda EROL, Mine ÖZDEMİR
Eskisehir Osmangazi University, Faculty of Engineering, Department of Chemical Engineering,
26480, Eskisehir
Hydrogen is considered to be an efficient energy carrier for the future due to
increasing demand of energy along with depletion of conventional fossil fuel reserves.
Borohydrides are the most promising source to produce clean H2 gas with very high
rate at room temperature. Among the chemical borohydrides, sodium borohydride
(NaBH4) is more favorable due to its advantages of high hydrogen density (10.8 %) and
stability in alkaline solution [1]. To increase and control the H2 generation rate through
hydrolysis of borohydrides an efficient and durable catalysts are necessary, made up of
elements that are abundant in our earth. Interest in Co-based catalysts, mainly cobalt
boride (Co-B), arises by their special features that make them potential catalyst for H2
production [2].
In this study, CoB catalysts were synthesized on the sepiolite by impregnation using
cobalt (II) chloride solution and then were reducted by sodium borohydride solution.
The Co loadings in catalysts used in this study were 10wt. % and 15wt. %. The hydrogen
generation activity of Co-B/sepiolite catalysts was tested through hydrolysis of sodium
borohydride alkaline solution. Effects of NaBH4 concentration and reaction temperature
on hydrogen generation rate were investigated. As the NaBH4 concentration increases
from 0.13 M to 0.33 M the hydrogen generation rate rises 3007.9 to 5863.2 mL/min
gCoB and 4013.67 to 10981.5 mL/min gCoB for catalysts containing 10wt % and 15wt %
Co, respectively. The hydrogen generation rate increases from 1438 to 5863 mL/min
gCoB and 3152 to 10982 mL/min gCoB for catalysts containing 10wt % and 15wt % Co,
respectively, with increasing reaction temperature from 30 °C to 50 °C.
References
[1]. Patel, N., Antonio, M., Progress in Co-B related catalyst for hydrogen production by hydrolysis
of boron-hydrides: A review and the perspectives to substitute noble metals, International Journal
of Hydrogen Energy, 2015, 1429-1464.
[2]. Özdemir, E., Enhanced catalytic activity of Co-B/glassy carbon and Co-B/graphite catalysts for
hydrolysis of sodium borohydride, International Journal of Hydrogen Energy, 2015, 1404514051.
109
Oxygen reduction and oxygen evolution reaction performances
of PtNi/CuO catalyst for lithium-air batteries
Gamze BOZKURTa,b, Tansel ŞENERb, Dino TONTIc, A. Kadir ÖZERa,d, Ayşe BAYRAKÇEKEN
YURTCANa,d
a
Atatürk University, Nanoscience and Nanoengineering Department, 25200, Erzurum,Turkey
b
TUBITAK, Marmara Research Center, Energy Institute, 41470, Kocaeli, Turkey
c
The Spanish National Research Council (CSIC), 28006, Serrano, Madrid, Spain
d
Atatürk University, Chemical Engineering Department, 25200, Erzurum, Turkey
Energy is a very important part of both the universe and our daily lives. Especially, clean
and high energy have a place in modern automotive industries. Therefore metal-air
batteries have been promising such as Al–air, Li–air, Mg–air, Fe–air, and Zn–air. One
of these types of batteries Li-air batteries have high energy potential for commercial
applications [1]. In recent years, various catalysts have been developed for Li-air
batteries. In this context, literature studies have focused on bifunctional catalysts that
are cheap and abundant transition metals for oxygen evolution reaction (OER) and
oxygen reduction reaction (ORR) in Li-air batteries [2].
In this study, CuO supported PtNi catalyst was prepared by using microwave irradiation
technique. In order to synthesize PtM (M;metal) on the supporting material various
methods such as impregnation, polyol, solverthermal, sputtering and nanocapsule have
been investigated. One of these methods microwave-irradiation technique is used in
this study for catalyst preparation. In the studies carried out in the literature, it was
observed that PtNi catalyst is effective for ORR and CuO catalyst is effective for OER
[3]. In this context, preparation of PtNi catalyst on CuO support material is achieved
by microwave irradiation. This catalyst is tested for charge and discharge capacity in
Li-air battery. The cycle-life tests will be also done to check the impact of the catalyst.
Physicochemical and electrochemical characterizations of the prepared catalysts were
performed.
Acknowledgements
The authors are gratefully acknowledge the financial support of Scientific Research Projects
Committee of Atatürk University with grant number of 2012/114.
References
[1] Akhtar N., Akhtar W., Int. J. Energy Res., 39 (2015) 303–316.
[2] Jung K., Riaz A., Lee S., Lim T., J. Power Sources, 244 (2013) 328-335.
[3] Hyun K., Lee J.H., Yoon C.H., Kwon Y., Int. J. Electrochem. Sci., 8 (2013) 11752 - 11767.
110
Preparation of Ni Catalyst on Co3O4 Support Material for H2
Production
Gamze BOZKURTa,b, Ayşe BAYRAKÇEKEN YURTCANa,b, A. Kadir ÖZERa,b,
a
Atatürk University, Nanoscience and Nanoengineering Department, 25200, Erzurum,Turkey
b
Atatürk University, Chemical Engineering Department, 25200, Erzurum, Turkey
The drawbacks of fossil fuels to the environment and human health have led to the
quest of cleaner fuels. For this reason, hydrogen (H2) as a renewable energy source and
environmentally friendly fuel has been gained increasing importance. H2 has the highest
energy content per unit mass at known fuels. At systems using hydrogen as fuel released
only water and water vapour to the atmosphere. Therefore, the hydrogen production is
quite important and a strategic issue [1].
Catalyst preparation is an important study area for H2 production from sodium
borohydride (NaBH4) which is safe and highly productive. Metallic catalysts that
transfer electrons to the molecular H2O to generate hydrogen are used for this purpose.
Behaviour of catalysts such as cobalt (Co) and nickel (Ni) are investigated for BH4hydrolysis. BH4- adsorption on the catalyst (M=Co, Ni) was observed [2].
Various methods have been used such as dip coating, impregnation, electroplating,
hydrogel, electroless plating etc. for catalysts preparation in the literature. One of these
methods microwave-irradiation technique is both efficient and time saving. Co3O4
prepared with microwave-irradiation technique can be used as support material for
metals as well as it is an effective catalyst for H2 generation [3]. In this study, Ni catalyst
on Co3O4 support material was synthesized by using microwave-irradiation technique
for H2 production from NaBH4 and physicochemical characterizations were performed
for the synthesized catalysts in order to determine the properties of the catalysts.
Acknowledgements
The authors are gratefully acknowledge the financial support of Scientific Research Projects
Committee of Atatürk University with grant number of 2015/360.
References
[1] Dutta S., J. Ind. Eng. Chem. 20 (2014) 1148–1156.
[2] Liu B.H,. Li Z.P., J. Power Sources, 187 (2009) 527–534.
[3] Hung T.F., Kuo H.C., Tsai C.W., J. Mater. Chem., 21 (2011) 11754-11759.
111
Syntheses and Characterization of Ni Containing Silica
Microspheres
Gamze Gunduz Meric, Levent Degirmenci
Bilecik Seyh Edebali University, Chemical and Process Engineering Department, 11100, Gulumbe
Campus, Bilecik.
Ni-based catalysts have long been investigated for their potential use in industry.
However, the sintering of Ni particles and carbon deposition are major problems
preventing their utilization [1]. Studies in recent years to develop highly active and
stable catalysts are of vital importance [2]. Noble metal bases catalysts, such as Rh, Ru,
Pt, Pd have good catalytic activity at the expense of high price [3]. As an alternative, Fe-,
Co- and Ni-based catalysts have drawn attention due to their high activity [4]. Ni-based
catalysts are the most promising because of their low cost, high selectivity and good
activity.
In this study, we investigate core-shell Ni containing microspheres prepared by a
modified sol- gel method. Initially varying amounts of Ni (10, 5, 1.25, 1 and 0.75 wt.
%) were dispersed into 20 ml deionized water, ultrasonicate for 15 min, and then
homogeneously dispersed in a mixture of 50 ml ethanol, 10 ml 25 wt. % ammonia
aqueous solution. 5 ml of TEOS was added to this solution. After stirring at room
temperature for 6 h, the product was washed with ethanol and deionized water for 3
times, centrifuged and dried at room temperature for 24 h. The structure of the samples
was characterized by X- ray diffraction (XRD), scanning electronic microscopy (SEM).
Surface area of the samples were determined using Brunauer-Emmett-Teller (BET)
method. Pore volume and pore size of the catalysts were derived using Barrett- JoynerHalanda (BJH) method. Finally, metal loading of Ni was determined using an Inductively
Coupled Plasma (ICP) Method.
References
[1] J. Liu, H. Peng, W. Liu, X. Xu, X. Wang, C. Li, W. Zhou, P. YYuan, X. Chen, W. Zhang, HH.
Zhan, ChemCatChem 6 (2014), 2095- 2104.
[2] Odedairo T, Chen J, Zhu Z. Catal Commun (2013) 31:25- 31.
[3] A. Erdöhelyi, J. Cserenyi, F. Solymosi, J. Catal. 141 (1993) 287–299.
[4] Yu M, Zhu Y-A, Lu Y, Tong G, Zhu K, Zhou X. Appl Catal B (2015)165:43- 56.
112
NEW DYE-SENSITIZIED Cu(I) COMPLEX PHOTOCATALYSTS
BEHAVIOUR ON PHOTOELECTROLYSIS
Gurbet YERLİKAYAa, Fatih TEZCANa, Gülfeza KARDAŞa, Osman SERİNDAĞb
b
Kanuni University, Institute of Science and Technology, 01170, Adana,
a
Increasing of energy necessity all over the world has motivated to researchers who new
clean and renewable energy application systems. Photoelectrochemical(PEC) water
splitting using with ZnO semiconductor has been extremely interested because of
environmentally produce H2 from water utilizing abundant plenty solar energy[1, 2]. On
the other hand, ZnO nano materials have need to improve in order to H2 production
at the lower bias potential for water photoelectrolysis. Within this framework our
study aim, photoluminescence(PL) of ZnO nanorods has been enhanced firstly using
4,4’,6,6’-terakis(N,N-ethlyaminostril)-[2,2’]bipyrimidineCu(I)aminomethlydiphospine as
organic dye-sensitized. Photoelectrochemical (PEC) measurements were carried out in
a convenient three-electrodes cell, an electrochemical analyser Gamry (interface 1000)
and a 300W Xe lamp solar simulator (100 mW/cm2). PL properties of ZnO films and
dye-sensitizied ZnO films have been examined with Flurorescence Spectrometer LS 55.
Dye-sensitizied ZnO nanorods are higher photocurrent density and emission intensity
than bare ZnO nanorods.
Figure
1.
Molecule
structureofa)4,4’,6,6’-terakis(N,N-ethlyaminostril)[2,2’]
bipyrimidineCu(I)aminomethlydiphospine b) PL spectra of Cu(I) complex covered
ZnO film and bare ZnO film
The authors are greatly thankful to The Scientific and Technical Research Council of
Turkey(TUBITAK) for financial support (Project No. 114R023).
References
[1] R. Lv, T. Wang, F.L. Su, P. Zhang, C.J. Li, J.L. Gong, Nano Energy, 7 (2014) 143-150.
[2] M.F. Shao, F.Y. Ning, M. Wei, D.G. Evans, X. Duan, Advanced Functional Materials, 24 (2014)
580-586.
113
THE CONVERSION OF CELLULOSE TO 5-HYDROXYMETHYL
FURFURAL (HMF) WITH ZEOLITE CATALYSTS
Esra Sezgin, Merve Esen, Solmaz Akmaz, Serkan Naci Koç, M. Ali Gürkaynak
Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcılar,
İstanbul
Fossil fuel resources are limited and depletion concern of resources in recent years has
increased interest in alternative energy production. Cellulose is known as the most
extensive renewable carbon-containing feedstock on earth. Therefore cellulose has the
potential to be source for the manufacture of many chemicals. The implementation
of new techniques and the development of catalytic processes made cellulose an
important source for production of a variety of chemicals, especially fuel production,
so the interest in studies on the production of alternative fuels from cellulose has
increased [1].
5-hydroxymethylfurfural (HMF) is one of the most important intermediate products
that lead cellulosic materials to fuel chemicals. From a commercial point of view, a
multifunctional compound HMF, among other biomass-derived materials, has attracted
attention due to being a major building block for the pharmaceuticals, plastics and fuels
since the last years of the 19th century [2,3].
The proposed work aims the design of solid acid catalysts which will be effective for
the conversion of cellulose to HMF, will not require the use of dissolved catalyst in the
reaction mixture. Support material was used as the porous structures such as zeolite.
The metal amounts of catalysts and phase structures were determined with ICP-MS
and X-Ray Diffraction (XRD), respectively. XPS and NH3-TPD techniques are also used
for characterization. The conversion of HMF from cellulose was studied at different
temperatures and time in the solvent medium. HMF was analyzed at High-Performance
Liquid Chromatography (HPLC) instrument.
The production of any type fuel additives as an alternative to fossil fuels having limited
resources, will contribute economically.
Acknowledgments
This study was supported by The Scientific and Technological Research Council of Turkey
(TUBITAK), project No: 214M149
References
[1] Yabushita M., Kobayashia, H., Fukuoka A. Applied Catalysis B: Environmental, 145, (2014) 1– 9
[2] Tong, X., Ma, Y., Li, Y. Applied Catalysis A: General, 385, (2010) 1–13.
[3] Hu, L., Zhao, G., Hao, W., Tang, X., Sun, Y., Lin L., Liu S. RSC Advances, 2, (2012) 11184–
11206
114
Oxidative Steam Reforming of Biogas by over NiCe/MgAl
Hydrotalcite-like catalysts
Merve Doğan, a,b Orhan Özcan, a,b Murat Efgan Kibar, a,b Ayşe Nilgün Akın
a
Kocaeli University, Department of Chemical Engineering, 41380, Kocaeli,
b
AYARGEM, Alternative Fuels R&D Center, Kocaeli University, 41040, Kocaeli,
a
In the future, energy systems will need to be cleaner, more reliable, much efficient and
sustainable. Hydrogen is a promising energy carrier and considered to be one of the
best candidates to use instead of fossil fuels. Nowadays, methane is the main source
for the production of hydrogen. Methane is usually supplied from natural gas. In recent
years, biogas pointed out as alternative source of methane to produce hydrogen [1].
In hydrogen production processes, tri-reforming process offers the most important
potential for economical and efficient conversion of biogas to hydrogen, due to the
high conversion, high selectivity and adjustable H2/CO molar ratio [2].
In this study, NiCe/MgAl Hydrotalcite-like catalysts (Ni content: 10 wt.% and Ce
contents: 2.5/5/7.5/10 wt.%) were prepared by wet impregnation and coprecipitation
methods and tested in tri-reforming reaction of model biogas to produce hydrogen.
XRD and BET technologies were conducted to characterize the catalysts. The reactions
were performed in a fixed-bed quartz reactor at 800 oC under atmospheric pressure.
The catalysts were studied under the reaction conditions of the feed gas molar ratios
of CH4/CO2/O2/H2O = 1/0.67/0.1/0.3. The reactor was inserted in an insulated electric
furnace, controlled by a programmable temperature controller. A K-type thermocouple
was placed into the middle of the catalyst bed to control the bed temperature. The
gaseous feed was controlled by mass flow controllers and steam was supplied to the
gaseous feed by using an isocratic pump. The products of the reactions analyzed by a
gas chromatograph equipped with FID and TCD. The results show that NiCe/MgAl
Hydrotalcite-like catalyst is a promising catalyst to obtain high H2 yield.
References
[1] U. Izquierdo ., V.L. Barrio., J. Requies., J.F. Cambra., M.B. Güemez., P.L. Arias., International
Journal of Hydrogen Energy, 7623-7631 (2013) 38.
[2] Pino L., Vita A., Lagana M., Recupero V., Applied Catalysis B: Environmental, 91-105 (2014)
148-149.
115
Microwave Assisted COx-free Hydrogen Production over
Mesoporous Carbon Supported Molybdenum Nanocatalysts
Melih GÜLER1 Dilek VARIŞLI1 Timur DOĞU2
GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey
Middle East Technical University, Department of Chemical Engineering, 06500, Ankara, Turkey.
1
2
In recent years, utilization of hydrogen as an alternative energy source by means of fuel
cell increases steadily, due to its energy content and its clean fuel properties [1]. Ammonia
is regarded as a prospective hydrogen carrier because of its favorable properties for onsite hydrogen generation and its decomposition produce only nitrogen as a by-product
[2]. Nowadays, microwave heating has gained great attention in reaction systems [3]
due to the efficient heating of active sites present in the catalyst which resulted in
higher conversion at lower reaction temperatures.
In this work, microwave assisted ammonia decomposition reaction was carried out
over mesoporous carbon (MC) supported Molybdenum(Mo) incorporated catalysts.
Carbon, is selected as a supporting material due to its good dielectric properties
andMolybdenum (Mo) was loaded at 5-15 wt % onto this support by following
impregnation procedure. Synthesized catalysts in their calcined, reduced and used
form were characterized with different techniques. Results of experiments that were
carried out in Microwave reactor system with GHSVNH3of 36,000 ml/hgcat showed that
32% ammonia conversion could be seen at 350oC and total conversion was achieved
at 400oC. In the literature, application of microwave heating on hydrogen production
from ammonia decomposition reaction cannot be found, and studies that include
conventional heating indicate higher temperatures, over 600oC, to obtain total
conversion over Mo incorporated mono-bi metallic supported catalysts [4,5].
Acknowledgement
References
[1] A. Kirubakaran, S. Jain, R.K. Nema, Renew. Sustain. Energy Rev. 13 (2009) 2430.
[2] Kaname Okura, Takeou Okanishi, Applied Catalysis A: General 505 (2015) 77–85
[3] S. Gündüz, T. Dogu , Applied Catalysis B: Environmental 168-169 (2015) 497–508
[4] B. Lorenzut, T. Montini, M. Bevilacqua, P.Fornasiero, Applied Catalysis B: Env. 125 (2012) 409–
417
[5] X. Duan, G. Qian, X. Zhou, D. Chen, W. Yuan,Chemical Engineering Journal 207–208 (2012)
103–108
116
HYDROGEN GENERATION FROM AMMONIA BORANE HYDROLYSIS
CATALYZED BY CoPd NANOPARTICLES
Nihat Tunça, Bayram Abaya, Murat Rakapb,
a
Yuzuncu Yil University, Department of Chemistry, 65080, Van
b
Yuzuncu Yil University, Maritime Faculty, 65080, Van
Ammonia borane (NH3BH3, AB) has extensively been employed as solid hydrogen
storage material over the last ten years due to its features like quite high hydrogen
content (19.6 wt%), high solubility in water, and high stability of its aqueous solution
[1]. AB releases 3 moles of hydrogen gas upon hydrolysis in the presence of suitable
metal catalsysts in aqueous solution. Up to date, a vast number of catalyst systems
have been used for the hydrolysis of ammonia borane, and more recently especially
bimetallic catalysts are focused on. With the addition of second element to the catalyst
structure, catalytic activity increases drastically [2].
In this study, PVP-stabilized cobalt-palladium nanoparticles were synthesized and
characterized by UV-VIS spectroscopy, TEM, XRD, and XPS techniques. The catalytic
activity of CoPd@PVP nanoparticles in the hydrolysis of ammonia borane was
investigated.
References
[1] Xu, Q., Chandra, M. J. Power Sources 163 (2006) 364-370.
[2] Chen, G., Desinan, S., Nechache, R., Rosei, R., Rosei, F., Ma, D. Chem. Commun. 47 (2011)
6308-6310.
117
EFFECT OF REACTION TEMPERATURE ON COKE FORMATION IN
DRY REFORMING OF METHANE
Hüseyin Arbağa, Sena Yaşyerlia, Nail Yaşyerlia, Gülşen Doğua, Timur Doğub
a
Department of Chemical Engineering, Gazi University, 06570 Ankara, Turkey
b
Department of Chemical Engineering, METU, 06800 Ankara, Turkey
Production of syngas from biogas through dry reforming of methane attracts researchers
due to its reducing effect of CO2 and CH4 emissions. Syngas may then be converted into
various fuels and chemicals. Research on dry reforming mainly focus on developing
highly active and stable catalysts with low coke formation. In our earlier studies it was
observed that modification of Ni catalysts by Rh, Ru and W improved coke resistance
of the catalyst [1-4]. In the present study, effect of reaction temperature on coke
formation on the surface of %8 wt Ni on mesoporous alumina catalysts (8Ni@SGA)
was investigated. Synthesized material had type IV adsorption-desorption isotherms.
In the XRD pattern of 8Ni@SGA, peaks which belong to -alumina and metallic Ni were
observed. The reactions were carried out in a fixed bed flow reactor at a space time of
0.1 s.g.cm-3 at different reaction temperatures, namely at 600oC and 750oC. The catalysts
showed stable performance during reaction time of four hours at both temperatures.
Increase of the reaction temperature from 600oC to 750oC increased the fractional
conversion of methane (0.26 at 600oC and 0.75 at 750oC) and carbon dioxide (0.38
at 600oC and 0.85 at 750oC). Higher fractional conversion of carbon dioxide than the
fractional conversion of methane obtained was due to the occurrence of reverse water
gas shift reaction together with dry reforming of methane. TGA analysis of used catalysts
also showed that weight loss (%33) at reaction temperature of 600oC was much higher
than weight loss (%12) at reaction temperature of 750oC, indicating significant decrease
in coke formation with an increase in reaction temperature. This result is also supported
by XRD patterns of the used catalysts.
References
[1] H. Arbag, S.Yasyerli, N. Yasyerli, G. Dogu, T. Dogu, I. G. O. Črnivec, A. Pintar, Ind. Eng. Chem.
Res., 54 (2015) 2290−2301.
[2] H. Arbag, S. Yasyerli, N. Yasyerli, T. Dogu, G. Dogu, Topics in Catalysis 56 (2013) 1695-1707.
[3] S. Yasyerli, S. Filizgok, H. Arbag, N. Yasyerli, G. Dogu, Int. J. Hydrogen Energy 36 (2011) 48634874.
[4] H. Arbag, S.Yasyerli, N. Yasyerli, G. Dogu, Int. J. Hydrogen Energy 35 (2010) 2296-2304.
118
THE ROLE OF PRECIOUS METALS ON ADSORPTION/DESORPTION
KINETICS OF OXYGEN OVER REDUCIBLE OXIDES
Deniz Kayaa, Dheerendra Singha, Deniz Üner*,a
a
Middle East Technical University, Chemical Engineering, 06800, Ankara, TURKEY
In this study, 1 wt. % Pd/CeO2-Al2O3 oxides with CeO2:Al2O3 wt:wt ratios of 10:90, 15:85
and 20:80 were synthesized by sequential impregnation of CeO2 and Pd. Temperature
programmed reduction (TPR), temperature programmed oxidation (TPO) and
temperature programmed thermal decomposition (TPtD) experiments were
performed by using Micromeritics Chemisorb 2720 TPR experiments revealed that for
CeO2 coated alumina samples with 10 % and 15 % CeO2 loading, surface reduction
peak of ceria was observed nearly at 600 °C, however bulk reduction peak of ceria could
not be observed. TPtD experiments performed upto 950 °C did not reveal any thermal
dissociation resulting in oxygen release over CeO2-Al2O3.TPR of the mixed oxides
indicated the absence of the reduction characteristic peak from the bulk ceria, while
the intensity of the surface related peaks starting at 300 °C increased with increasing
ceria amount. The amount of the oxygen released during TPtD did not change with
ceria loading much.
Figure 1. TPR (left) and TPtD (right) spectrum of 1 % Pd/CeO2-Al2O3 samples at 20 °C/
min heating rate
Heat of adsorption of oxygen was measured using a Setaram C-80 Tian-Calvet
microcalorimeter. Heat of adsorption at the saturation coverage of 2.41 μmole O2/gcat.
and 1.93 μmole H2/gcat. for 1 wt. % Pd/CeO2 was 478 and 154 kJ/mol respectively.
Acknowledgement
This project is financially supported by TÜBİTAK 213M006 project under the leadership of Assoc.
Prof. Serkan Kıncal.
119
MODELING OF DATABASE CONSTRUCTED FROM PUBLISHED
ARTICLES FOR WATER SPLITTING OVER PEROVSKITES
Elif Cana, Ramazan Yıldırımb,
a
b
Boğaziçi University, Department of Chemical Engineering, 34342 Bebek, Istanbul
Boğaziçi University, Department of Chemical Engineering, 34342 Bebek, Istanbul
The aim of this work was to extract useful knowledge from published articles for
photocatalytic water splitting over perovskite-type catalysts, then to examine whether
the result of an unperformed experiment can be estimated, or whether the best
conditions for the future works can be determined in advance. For this purpose, the
articles published from 2005 to 2014 about PWS in the literature were studied. A
comprehensive database involving 2704 instances was constructed from those articles
available in online libraries. The hydrogen production rate (µmol/g-cat/h) was selected
as output variable, and it was tried to be estimated by using input variables related to
catalytic or operational variables. During the generation of the database, it was observed
that the interest on PWS studies has been aroused since 2000s as it is evident from
Figure 1. Different data mining tools and models were developed and utilized in “R”
environment. The data for ABO3 and ABS3 type perovskites were modelled separately,
and the best predictions were obtained with “random forest” technique. The plot of
predicted vs. observed hydrogen production rate for ABO3 perovskites is given in Figure
2 as example.
Figure 1. Number of Published Articles
on PWS vs. Years
Figure 2. Results of Best Performed Model
Analysis was indicated that the operational variables seem to be more influential for
hydrogen evolution. Nb (as B site of perovskite) and K (as A site of perovskite) were
determined as relatively more effective compare to the other elements.
120
MORPHOLOGY OF PT-CU NANOPARTICLES BY USING GENETIC
ALGORITHM AND DENSITY FUNCTIONAL THEORY
Ezgi ERDEMa, Rıza KIZILELb, Can ERKEYa,b
a
Koç University, Chemical and Biological Engineering Department, Sarıyer 34450, Istanbul
b
Koç University, Koç University Tupraş Energy Center (KUTEM), Sarıyer, 34450, Istanbul
Supported bimetallic nanoparticles can provide enhanced activity and selectivity
compared to their pure counterparts in many reactions catalyzed by heterogeneous
catalysts. The morphology of these nanoparticles plays a very important role in how
a particular catalytic cycle proceeds. Carbon supported Pt-Cu nanoparticles show
promise for use as electrocatalysts in polymer electrolyte membrane fuel cells. In this
study, we investigated the morphology of Pt-Cu clusters by computational chemistry
methods. One of the most effective optimization approaches for finding the structure
of a cluster with the minimum energy level is Density Functional Theory (DFT)
which allows a close connection between theory and experiment and often leads
to important clues about the geometric, electronic and spectroscopic properties of
the systems being studied. Essential part of working under DFT environment is the
identifying initial structure of cluster qualitatively, because of feeding locally optimized
structures rather than randomly arranged structures to DFT, reduces processing time
and provides energetically stable clusters at global minima. In this study, the locally
optimized structures of Pt-Cu bimetallic clusters (1:1 composition for N=10-40 atoms)
were searched using Genetic Algorithm (GA) by using Gupta potential which is based
on second moment approximation to tight binding theory. GA was used to solve a
series of attractive and repulsive potential energy equations and find which morphology
gives a minimum potential. The energy scaling parameters for Gupta potential which
are A, 𝜉, p and q describing heteronuclear Pt-Cu interactions, were obtained by taking
weighted averages of these parameters for pure bulk Pt and Cu metals. Then, the lowest
energy structures which were found empirically were reoptimised at the ab-initio DFT
level (first principles). DFT calculations were carried out using Gaussian 09 quantum
chemistry simulation package within a LANL2DZ basis, and B3PW91 exchange
correlational function (Becke Three Parameters Hybrid Function). The structural motifs
calculated by Gupta potential, as a function of composition and weighted parameters,
were similar with structures obtained by DFT but the distances and places of certain
atoms were different. The structures predicted by combination of GA and DFT are
randomly chemically disordered structures as minimum energy states with no apparent
segregation of a particular species either to the core or to the surface.
121
TEMPERATURE EFFECT ON THE CARBON DIOXIDE SORPTION
CAPACITY OF NATURAL MAGNESITE DERIVED SORBENT
Dilsad Dolunay Eslek Koyuncua, Sena Yasyerlia,Nail Yasyerlia,
Chemical Engineering Department,Gazi University, 06570, Ankara
a
Due to the significant increase in atmospheric CO2 concentration, the removal of CO2
has become an important global issue in the field of energy and environment [1].
Natural minerals (such as dolomite and limestone) have been used conventionally
because of its availability and low cost, high CO2 capture capacity and suitable
reaction kinetics [2, 3]. The aim of this study is to investigate the CO2 sorption capacity
of natural magnesite mineral as sorbent due to its high MgO content and availability
in Turkey.
XRF results showed the presence of nearly 80 wt % MgO in the raw mineral structure.
It is expected that MgO is mainly active phase for CO2 sorption at low temperatures.
MgCO3-magnesite and CaMg(CO3)2-dolomite phases were detected in the XRD
patterns of natural magnesite mineral.In the TGA-DTA analysis, decomposition of
carbonate species were observed within the following ranges of 500-670 0C and 670830 0C, respectively.At the end of characterization studies magnesite mineral was
calcined at 900 0C (3 0C/min, 3 h).Before calcination step natural magnesite mineral
was finely ground to obtain powder (< 0.7 mm).Surface area of the calcined sorbent
was found to be 23 m2/g and MgO and small amount of CaO phases were detected
by XRD. CO2 capture tests were performed in a fixed bed reactor system using feed
stream containing 4% CO2 in He with a GHSV of 3600 cm3h-1g-1 at temperature range
of 35-400 0C.CO2 sorption capacity of the magnesite mineral sorbent was decreased
by increase in sorption temperature. The highest CO2 sorption capacity of magnesite
derived sorbent was found as 0.18 mmol CO2/g sorbent at 35 0C using breakthrough
analysis.
References
[1] Zhang, Z., Xu, M., Wang, H., Li, Z., Chemical Engineering Journal, 160 (2010) 571-577.
[2] Wang, K., Zhao, P., Guo, X., Han, D., Chao, Y.,Energy Conversion and Management, 86 (2014)
1147-1153.
[3] Mastin, J., Aranda, A., Meyer, J.,Energy Procedia, 4 (2011) 1184–1191.
122
PREPARATION SUPPORTED PT AND RU CATALYSTS AND THEIR
PERFORMANCES IN AVPR PROCESS
Bahar Meryemoglua, Mehtap Kurtulusa,Arif Hasanoglua, Sibel Irmakb
Cukurova University,Chemistry, 01330, Adana
University of Nebraska-Lincoln, Biological Systems Engineering, 68583, Lincoln, USA
a
b
Precious metal catalysts are widely used in the supported form on porous materials
such as activated carbon, alumina, silica, silica-alumina, various organic polymers, and
so forth, with a variety of properties (e.g., particle size, surface area, pore volume and
size, mechanical strength and resistance to attrition, thermal stability, etc.) [1].In this
study, alumina, silica and activated carbon (AC) supported Pt and Ru catalysts were
prepared and the effect of support material and metals investigated in atmospheric
pressure catalytic vapor phase reforming (AVPR) for lignocellulosic biomass. The
characterization of catalysts were investigated with XRD, BET, TEM and the structure
of samples were also investigated using FTIR, GC-TCD and GC-MS. The BET surfaces of
supported materials showed differences.
Activated carbon has the highest BET surfaces area (951 m2/g), while alümina has the
lowest (190 m2/g). TEM analysis results that Pt and Ru particles loaded uniformly on
support material and there was no sintering. However, it was observed that Pt and Ru
particles loaded on silica dispersed as a stack. The gas volume of supported catalysts
were 30.0, 25.0 and 15.0 ml for activated carbon, alumina and silica, respectively. The
order of gasification effiency and hydrogen yield was as AC > Alumina > Silica. The
activity of AC supported catalysts (Pt-AC and Ru-AC) were most efficent because of
that activated carbon support had the highest surface area among the other supports.
The 13.4 ml H2/g catalyst was produced when Ru-AC was used as catalyst in AVPR.
Alumina support with the lowest BET surface area produced high hydrogen selectivity
13.7 ml H2/g catalyst as much as activated carbon. Silica supported catalysts showed
the lowest performance in gasification.
Acknowledgement
Financial support from Scientific and Technical Research Council of Turkey (TUBITAK) is gratefully
acknowledged (The project number: 114M146).
References:
[1]Kaya B, Irmak S, Hesenov A, Erbatur O, Erkey C. Bioresour Technol 2012;123:723–6.
123
Investigation of Metal Loading Ratio Effect on Characteristics of
Co/Al2O3 Catalysts and Utilization in Catalytic Pyrolysis
Nurgül ÖZBAYa, Pınar BAŞa, Adife Şeyda YARGIÇa
BilecikŞeyhEdebali University, Faculty of Engineering, Chemical and Process Engineering
Department, 11210 Bilecik
a
Supported Co catalysts are often used for many catalytic reactions such as Fischer
Tropsch synthesis, pyrolysis, oxidation reactions, etc. due to their good activity and
selectivity[1-3].Catalytic pyrolysis is a promising method for the direct conversion of
solid biomass into fuel andvaluable chemical feedstocks [4]. Catalytic pyrolysis process
provides to obtain desired product yields and improve the bio-oil quality. Besides,
catalytic effect of additives can reduce the initial devolatilization temperature and the
char formation.A variety of catalysts have been studied for the catalytic pyrolysis of
biomass, such as ZSM-sulfated metal oxides, Al-MCM-41, SBA-15, and noble metal
catalysts. Among these catalyts, cobalt-based catalysts have potential to use in catalytic
pyrolysis reactions [2].
In this study, catalysts with different cobalt loading ratio (5 and 10 wt. %) were prepared
by the co-precipitation method. The catalysts were characterized by SEM, XRD, and
BET method. The prepared Co/Al2O3 catalysts were used in tomato waste pyrolysis
at 500 °C and non-catalytic and catalytic pyrolysis product yields were compared.The
chemical compositions of liquid products were determined by GC–MS, FT-IR and
Elemental Analysis.
References:
[1] Visconti, C. G., Lietti, L., Tronconi, E., Forzatti, P., Zennaro, R., Finocchio, E. Applied Catalysis
A: General, 355(1) (2009), 61-68.
[2] Le, T. A., Ly, H. V., Kim, J. Energy Sources, Part A: Recovery, Utilization, and Environmental
Effects, 36(21) (2014), 2392-2400.
[3] Zhang, X. W., Shen, S. C., Hidajat, K., Kawi, S., Liya, E. Y., Ng, K. S. Catalysis Letters, 96(1-2)
(2004), 87-96.
[4] Carlson, T. R. (2010). Catalytic fast pyrolysis of biomass for the production of fuels and
chemicals.
124
AN EFFICIENT HETEROGENEOUS CR-ZEOLITE CATALYST FOR
GLUCOSE TO 5-HYDROXYMETHYLFURFURAL CONVERSION
Merve Esen, Esra Sezgin, Solmaz Akmaz, Serkan Naci Koç, M. Ali Gürkaynak
İstanbul Üniversitesi, Mühendislik Fakültesi, Kimya Mühendisliği Bölümü, 34320 Avcılar, İstanbul
Cellulose as a polysaccharide is the most abundant biomaterial in the world and its
bio-based products are considered to be one of the alternatives to many petroleum
products. The conversion of cellulose and glucose to valuable biorefinery products has
gained great importance in recent years [1-3].
The dehydration product of glucose and/or fructose is 5-hydroxymethyl furfural
(HMF). Five-membered ring compound HMF is one of the most important bio-based
so-called platform chemicals. The ring structure of glucose is more stable than that of
fructose and hence higher HMF yields are obtained from fructose with homogeneous
or heterogeneous acid catalysts. HMF is an important chemical that can be easily
converted to valuable furan derivatives, such as, high octane 2,5-dimethylfuran biofuel
compound [4].
In this study, CrCI3, H-zeolite and calcined Cr-zeolites were studied in the liquid phase
heterogeneous catalytic conversion of glucose to HMF in ionic liquids. Characterization
of catalysts were done in XPS, XRD and NH3-TPD. The prepared catalysts were tested
for the conversion of HMF from glucose at different temperatures and time in the
solvent medium. At the end of the reactions, the liquid product was analyzed at HighPerformance Liquid Chromatography (HPLC) instrument. A Little decrease in both
glucose conversion and HMF yield was observed with the addition of chromium (III)
chloride impregnated zeolite catalysts when compared to homogeneous CrCI3-[BMIM]
CI system. High glucose and HMF yields were obtained with heterogeneous calcined Crzeolite. Best HMF yield achieved was 58.8%.
Acknowledgments
This study was supported by The Scientific and Technological Research Council of Turkey
(TUBITAK), project No: 214M149
References
[1] Hu, S.; Zhang, Z.; Song, J.; Zhou, Y.; Han, B. Green Chem., 2009, 11, 1746-1749
[2] Takeuchi, Y.; Jin, F.; Tohji, K.; Enomoto, H. J Mater. Sci. 2008, 43, 2472-2475
[3] Hu, L.; Zhao, G.; Tang, X.; Wu, Z.; Xu, J.; Lin, L.; Liu, S. Bioresource Technol. 2013, 148, 501507
[4] Román-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Nature 2007, 447, 982-985
125
N-HETEROCYCLIC CARBENE-BASED NICKEL(II) COMPLEXESIN
KUMADA COUPLING
Deniz DEMİR ATLI, Şebnem E. SÖZERLİ
Celal Bayar University, Faculty of Arts and Sciences, Department of Chemistry, 45050, Manisa
Kumada cross coupling reaction has been widely used in organic synthesis to construct
biaryl compounds, which are important building blocks of functional materials, natural
products and medicines [1-3]. N-heterocyclic carbene nickel(II) complexes efficiently
catalyze these reactions [4-7].
In this study, threenew neutral N-heterocyclic carbene nickel(II) complexes of the
formula [(NHC)CpNiX] (X = Br, Cl) were synthesized by the reaction of nickelocene
with corresponding ester-functionalized benzimidazolium salts. The complexeswere
characterized by 1H NMR,13C NMR, FT-IR and elemental analysis methods.It was
found that nickel(II) complexes exhibited high catalytic activities in the cross-coupling
reactions of aryl chlorides and bromides with phenylmagnesium bromide at room
temperature.
References
[1] K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc., 94 (1972) 4374-4376.
[2] R.J.P. Corriu, J.P. Masse, J. Chem. Soc., Chem. Commun., (1972) 144.
[3] M. Kumada, Pure Appl. Chem., 52 (1980) 669-679.
[4] Z. Xi, B. Liu, W. Chen, J. Org. Chem., 73 (2008) 3954-3957.
[5] H.V. Huynh, R. Jothibasu, Eur. J. Inorg. Chem., (2009) 1926-1931.
[6] J. Berding, T.F. Dijkman, M. Lutz, A.L. Spek, E. Bouwman, Dalton Trans., (2009) 6948-6955.
[7] W. Guo, Z. Wang, J. Org. Chem., 78 (2013) 1054-1061.
126
Sorption Enhanced Steam Reforming of Ethanol Over Ni
Impregnated SBA-15 Catalyst
Merve Sarıyer, Arzu Arslan, Naime Aslı Sezgi, Timur Doğu
Chemical Engineering Department,Middle East Technical University, 06800, Ankara
Environmental concerns and fast depletion of fossil resources accelerated the research
and development activities for the production of alternative fuels and energy carriers.
Hydrogen has been considered as one of the most promising energy carriers for fuelcell-derived cars. Bio-ethanol is one of the most promising non-fossil resources for the
production of hydrogen [1, 2]. Thermodynamic limitations of steam reforming reaction
of ethanol cause reduction in hydrogen yield, in this process. In the present work, ethanol
reforming was performed in a sorption enhanced process, to increase hydrogen yield
by in-situ removal of produced CO2, using CaO as a sorbent. Ni impregnated SBA-15
was used as the reforming catalyst in this system. SBA-15 is a promising catalyst support
due to its ordered mesoporous silicate structure, high surface area and moderate
hydrothermal stability, while Ni has been shown to give high activity in reforming
reactions. Characterization results of synthesized materials showed that this catalyst
had a surface area of 856 m2/g and exhibited Type IV nitrogen adsorption/desorption
isotherm with H1 hysteresis loops, indicating mesoporous structure with ordered
pores. Comparison of the activity test results obtained in the presence and absence of
CaO sorbent revealed significant increase of hydrogen yield in the sorption enhanced
reforming test. Mole fractions of CO2 and CO in the product stream decreased from
0.12 to 0.2 and from 0.14 to 0.4, respectively, as a result of in-situ removal of CO2 in
the sorption enhanced process. Results proved the advantages of sorption enhanced
process for the production of high purity hydrogen from ethanol.
References
[1] Gunduz, S., & Dogu, T. (2012). Sorption-enhanced reforming of ethanol over Ni- and Coincorporated MCM 41 type catalysts. Industrial and Engineering Chemistry Research, 51(26),
8796–8805.
[2] Arslan, A., Gunduz, S., & Dogu, T. (2014). Steam reforming of ethanol with zirconia
incorporated mesoporous silicate supported catalysts. International Journal of Hydrogen Energy,
39(32), 18264–18272.
127
ESTERIFICATION OF GLYCEROL WITH OLEIC ACID over Ti
CONTAINING SULFATED SBA-15 CATALYSTS
Gamze AY, Giray MUTLU, Emre KILIÇ, Hasan ÖRTÜN, Selahattin YILMAZ
Department of Chemical Engineering, Izmir Institute of Technology, Izmir, Turkey
Production of biodiesel is based on the trans-esterification of vegetable oil and short
chain alcohol. Being a renewable resource, its use is increasing steadily. During this
process, glycerol is formed as a byproduct in large quantities. Also there is glycerol
formation in soap production. Glycerol formed can be converted to valuable product
glycerol monoesters (monoglycerides) which can be used as emulsifiers in food,
pharmaceutical and cosmetic industries. The aim of this study is to develop active and
selective heterogeneous catalyst for esterification of glycerol and oleic acid to obtain
monoglyceride. This reaction requires acidic catalysts.
In this study, titania containing sulfated SBA-15 catalysts with different Ti loadings (2%
and 6%) were prepared (SO4/TiSBA-2 and SO4/TiSBA-6). Sulfation process was carried
out by using ammonium sulfate solution. Esterification reaction was performed under
nitrogen flow in three necked glass reactor at 160 oC without using a solvent. Effect of
glycerol/oleic acid mole ratio (3 and 6) was also investigated.
The catalysts prepared were mesoporous and had high acidity. Higher titania loading
provided more sulfur bonding and improved the total and Brønsted acidity. The main
products were found as mono, -di, and triglycerides. The highest monoglyceride yield
was obtained over SO4/TSBA-6 catalyst as 49 % when conversion of oleic acid was 62
% after 5 h reaction time. It was found that catalyst with high acidity and Brønsted acid
sites were more active in esterification reaction and gave higher yield to monoglycerides.
Glycerol/oleic acid ratio affected the monoglyceride yield significantly. It was improved
from 49 % to 65 % by rising the glycerol/oleic acid mole ratio from 3 to 6. When excess
amount of glycerol was used, oleic acid reacts with unreacted glycerol instead of
monoglyceride, also equilibrium shifts towards the products. Thus, yield was improved.
128
Synthesis and Characterization of Perovskite Catalyst and Its
Catalytic Activity in Pyrolysis
Nurgül ÖZBAYa, Rahmiye Zerrin YARBAY ŞAHİNa
a
Bilecik Şeyh Edebali University, Faculty of Engineering, Chemical and Process Engineering
Department, 11210 Bilecik
Biomass has taken great attention as a clean and alternative energy source which has
advantages such as being renewable, emitting relatively low CO2 levels, and having
negligible amount of sulfur. Pyrolysis is thermal decomposition of biomass in the
absence of oxygen to achieve liquid (bio-oil), gas and char products[1-3]. Addition of
catalyst into the pyrolysis is one of the common upgrading method in order to improve
the bio-oil quality.
In this study, mandarin peel was used as a biomass source and pyrolysis was performed
to achieve bio-oil, gas and char products at the temperature of 550°C using 100°C/min
of constant heating rate and 100 ml/min of constant nitrogen gas (N2) flow rate. The
effect of catalyst (LaMnO3)on the product yields was investigated. The crystal structures
of catalysts were determined X-Ray Diffraction (XRD), morphology of the samples
were analyzed by Scanning Electron Microscope (SEM), and the specific surface area
of the samples were determined by nitrogen adsorption desorption isotherms (BET)
measurements.The chemical compositions of liquid products were determined by GC–
MS, FT-IR and Elemental Analysis.
References:
[1] Aysu T., Durak H., Güner S., Bengü A.Ş., Esim N., Bioresource Technology, http://dx.doi.
org/10.1016/j.biortech.2016.01.015
[2] Li, S., Zhu, J., Chen, M., Xin, W., Yang, Z., Kong, L., Int J Hyd Energ., 39 (2014),13128-35.
[3] Li, S., Xu, S., Liu, S., Yang, C., Lu, Q., Fuel Process Technol., 85 (2004), 1201-11
129
EPOXIDATION OF METHYL OLEATE OVER SO4/TiO2-SiO2 AND
WO3-ZrO2 CATALYSTS
Vahide Nuran Mutlua, Canan TAŞa, Selahattin YILMAZa
a
Izmir Institute of Technology, Chemical Engineering, Izmir Instıtute of Technology Chemical Eng.
Department Urla, Izmir Turkey
Diminishing petroleum resources increased the demand on development of alternative
and renewable sources. Epoxidized fatty acid esters are one of the key raw materials
for a wide variety of products. They are used for many commercial applications, as
plasticizers and stabilizers, as additives in lubricants, as components in thermosetting
plastics and in cosmetics and pharmaceutical formulations [1]. Industrially, epoxidized
fatty acids produced by the homogeneous peracid process.However, to fulfill the
environmental concerns, it is preferred to carry out these epoxidation reactions by
heterogeneous catalysts instead of homogeneous catalysts.In this work, methyl oleate
was produced byesterification of methanol and oleic acid using sulfuric acid as catalyst.
Methyl oleate produced was then epoxidized with hydrogen peroxide over SO4/TiO2SiO2 and WO3-ZrO2catalysts in ethyl acetate at 80oC. TiO2-SiO2 catalyst was prepared by
sol-gel and sulphated. WO3-ZrO2 was prepared by co-precipitation method. Catalysts
were characterized using BET, XRD and NH3-TPD methods. Characterization studies
showed that while WO3-ZrO2 smallersurface area and pore size compared to SO4/
TiO2-SiO2. Surface acidity studies showed thatWO3-ZrO2 possessed medium strength
acid sites while SO4/TiO2-SiO2had peaks at both weak andstrong acid sites. The methyl
oleate conversion obtained over SO4/TiO2-SiO2(35%) than WO3-ZrO2(24%). When the
results obtained over two catalysts were compared, it can be said that the acidity of the
catalyst is important for the activity.
References
[1] A. Campanella, M. A. Baltanás M. C. Capel-Sánchez, J. M. Campos-Martín J. L. G. Fierro,Green
Chemistry, 6 (2003) 330 – 334
[2] J. Sepulveda, S. Teixeria, U. Schuchardt, Applied Catalysis A: Gen. 318 (2007) 213 – 217
130
THE EFFECT OF PEROXIDE ON BIOMASS HYDROLYSIS AND
CATALYTIC GASIFICATION OF HYDROLYSATES
Mehtap Kurtulusa, Bahar Meryemoglua, Arif Hasanoglua, Sibel Irmakb
Cukurova University,Chemistry, 01330, Adana
University of Nebraska-Lincoln, Biological Systems Engineering, 68583, Lincoln, USA
a
b
The present study was designed to produce hydrogen gasin AVPR of lignocellulosic
biomass hydrolysates using peroxide. In this study, lignocellulosic biomass was
hydrolyzed in subcritical water condition in the absence and presence of peroxide and
was gasified with Raney Ni catalyst. The gaseous products were analyzed with GC-TCD
and liquid products were analyzed GC-MS.
The 88,5 ml gas volume of hydrolysate without peroxide obtained in AVPR. The
hydrogen yield of this hydrolysate was 5,7 ml H2 / g catalyst (Table 1). The total gas
volume and gas composition changed with the use of peroxide in hydrolysis. When
biomass hydrolysates were gasified by AVPR, hydrolysate with %0,5 H2O2 produced the
highest gas yield with high hydrogen selectivity (110,0 ml; 6,9 ml H2 /g catalyst). It was
observed that the gas volume and hydrogen yield of hydrolysate used in the AVPR
for hydrogen production decreased with increasing amount of peroxide in hydrolysis
process. This could be attributed to gasification of organic molecules during hydrolysis
in the presence of peroxide.
Table 1. Gasification of hydrolysates with different percentage peroxide using Raney Ni
catalyst
Acknowledgement
Financial support from Scientific and Technical Research Council of Turkey (TUBITAK) is gratefully
acknowledged (The project number: 114M146).
131
Palladium (0) Nanoparticles Supported on Amine-Functionalized
Silica for the Catalytic Hexavalent Chromium Reduction
Metin Celebia, Mehmet Yurderia, Ahmet Buluta, Murat Kayab, Mehmet Zahmakirana,*
Nanomaterials and Catalysis (NanoMatCat) Research Laboratory, Department of Chemistry,
Yüzüncü Yıl University, 65080 Van, Turkey
b
Department of Chemical Engineering and Applied Chemistry, Atilim University, 06836 Ankara,
Turkey
a
Hexavalent chromium (Cr(VI)) is commonly identified acutely toxic, a proven mutagen
and carcinogen heavy metal polluant in the aquatic environment, whereas Cr(III) is
believed to be essential element. In the present study, we show that palladium(0)
nanoparticles supported on 3-aminopropyltriethoxysilane (APTS) funtionalized silica
(Pd@SiO2-NH2) effectively catalyze te reduction of Cr(VI) to Cr(III) by using formic acid
(HCOOH) as reducing agent under mild conditions (at room temperature under air).
Pd@SiO2-NH2 catalyst was reproducibly prepared by deposition-reduction technique
and characterized by the combination of various spectroscopic tools including ICOOES, P-XRD, DR/UV-vis, XPS, BFTEM, HRTEM and TEM-EDX techniques. The sum of
their results is indicative of the formation of well-dispersed palladium(0) nanoparticles
(dmean= 3.7 nm) on the surface of APTS-functionalized SiO2. The catalytic performance of
the resulting palladium(0) nanoparticles in terms of activity and stability was evaluated
by the catalytic reduction of Cr(VI) to Cr(III) in aqueous solution in the presence of
formic acid as a reducing agent. Our results reveal that Pd@siO2-NH2 catalyst displays
unprecedented activity (TOF=258 mol Cr2O72- / mol Pd min) and reusability (<85% at
5th reuse) forthe reduction of Cr(VI) to Cr(III) at room temperature.
Figure 1.The photographs of the reaction solution for Pd@SiO2–NH2 catalyzed reduction of Cr(VI) to
Cr(III) by using formic acid (HCOOH) and formation of green hexahydroxochromate via addition of
excess NaOH.
132
PALLADIUM NANOPARTICLES(Pd NPs) AS EFFICIENT CATALYSTS
FOR SUZUKI-MIYAURA REACTION IN MILD CONDITIONS
Burcu DARENDELİa, Fatma Ulusala, Bilgehan GÜZELa
a
Chemistry Departmant, University of Cukurova, 01330 Adana, TURKEY
Recently, there has been great interest on the use of metal nanoparticles (NPs) for
nanocatalysis[1]. Palladium NPs have become of increasing scientific interest as catalysts
for carbon–carbon bond-forming reactions, such as Suzuki–Miyaura cross-coupling
reactions, which are among the most powerful methods in organic synthesis.These
reactions are typically performed under heating or at reflux [1,2]. Much less is known
about the room temperature Suzuki–Miyaura cross-coupling reaction catalyzed by
PdNPs. In this work, Suzuki-Miyaura cross-coupling reaction is performed at room
temperature and the conversion yields were nearly as same as the typical reaction
results. Performing the reaction under lower temperature is a huge advantage for
industrial processes cause of saving energy.
Figure 1. XRD pattern of Pd NPs
Pd NPs were prepared chemical impregnation method and the metal loading was
determined by ICP analysis. XRD and SEM analysis were used for characterization of
the prepared PdNPs (Fig.1.). The catalytic activities were performed in Suzuki-Miyaura
cross coupling reactions and the reactant/product ratio was determined with gas
chromotography (GC).
References:
[1] D. Astruc, Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008.
[2] J. Tsuji, Palladium Reagents and Catalysts, Wiley, New York, 2004.
133
Investigation of Isobutane Dehydrogenation in a Pd-membrane
Reactor
Saliha Çetinyokuş Kılıçarslanª, Meltem Doğanb, TimurDoğuc,
ª Republic of Turkey Disaster and Emergency Management Authority, Department of Planning and
Mitigation,06530 Ankara, Turkey
b
Gazi University, Chemical Engineering Department, 06570 Ankara, Turkey
c
Middle East Technical University, Chemical Engineering Department, 06800 Ankara, Turkey
Isobutane dehydrogenation is an endothermic equilibrium-limited reaction. In order
to overcome equilibrium limitations, produced hydrogen can be removed from the
reaction medium[1,2,3]. In this work, isobutane dehydrogenation was achieved in a
commercial Pd-membrane reactor system. Reaction was performed under fixed–
bed conditions using aCr/MCM-41 catalyst [4] (surface area: 990m2/g, averagepore
diameter: 2nm, containing 3% of Cr by mass), which was synthesized following a
hydrothermal route. Experimental studies were performed at different temperatures
(T=723K, 773K, 823K), using a pure isobutane feed stream (50ml/min, WHSV=28h-1).
Isobutane dehydrogenation was performed at a pressure difference of 70kPa across
the membrane. Isobutane conversion value of 25% was determined at873K. No side
reaction products (propane, propene, methane) were observed at 773K and 823K in
the membrane reactor. However, isobutenes electivity decreased to about 55% at 873
K, because of the occurrence of side reactions.All of the side reaction products were
observed in the experiment carried out in 873K and without catalyst. Experiments
performed in the membrane reactor without the Cr/MCM-41 catalyst showed that
Pd membrane itself was also a highly active catalyst for the occurrence of isobutane
dehydrogenation, as well as side reactions, especially at a high temperature (873
K). Results proved that produced hydrogen was first used in reduction of Cr6+and
significant information was obtained about the reaction mechanism.
References
[1] Sahebdelfar, S., MoghimpourBijani, P., Saeedizad, M., TahririZangeneh, F. and Ganji, K., Appl.
Catal., A, 395, 2011,107–113.
[2] Farsi, M., Jahanmiri, A., Rahimpour, M.R., J. Ind. Eng. Chem., 18, 2012, 1676–1682.
[3] Çetinyokuş Kılıçarslan, S., Doğan, M., Doğu, T., Int. J. Chem. Reactor Eng., DOI 10.1515/
ijcre-2015-0031, 2015.
[4]Kılıçarslan, S., Doğan, M., Doğu, T., Ind. Eng. Chem. Res.,52(10), 2013, 3674–3682.
134
PREPARATION OF NOVEL VIC-DIOXIME-Pd(II) COMPLEX FOR
SUZUKI-MIYAURA REACTIONS
Özge Atışa, Fatma Ulusala, Bilgehan Güzela
a
In the past two decades, a great number of coordination compounds were
synthesized for catalytic application onSuzuki-Miyaura and Heck reaction,
hydrogenation,hydroformylationof unsaturated substrates. Organophosphine
compounds are generally used as homogenous catalysis in Suzuki-Miyaura cross
coupling reaction. But usage of these compounds are limited for having environmental
damages.Pd(II) complexes of vic-dioxime can be used for Suzuki-Miyaura as an
alternative to organophosphine owing to non-toxicity and high activity. In this work,
novel vic-dioxime ligand (2-fluoroaniline-amphi-vic-dioxime) and Pd(II) complex were
synthesized and characaterized. Catalytic activities of the synthesized Pd complex were
investigated in Suzuki-Miyaura reaction of bromobenzene and phenilboronic acid.
Fig.1.Suzuki Miyaura reaction
Fig.2.Per cent conversion ratio of reaction
Suzuki-Miyaura experiments were carried out-at room temperature. The conversion
ratio was determinated by gas chromatography. In this experiments which has 1/1000
catalyst ratio,conversion close up to %100 has been observed in 45 minutes. We can
say, Pd(II) complexes of vic-dioxime can be used as catalyst in Suzuki-Miyaura reactions
according to these results.
This study have been supported by the The Scıentıfıc And Technologıcal Research
Councıl of Turkey (TÜBİTAK) (project no:214Z097).
References:
[1] Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483 [1].
[2] Suzuki, A. Diederich,F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998.
135
136
POTENTIAL APPLICATIONS OF SOLID SUPPORT CATALYTIC
MEDICAL MOLECULAR
Ümit YAŞARa, Fatma ULUSALb, Bilgehan GÜZELb, Pınar Yılgör HURİc, Nurten DİKMENa
Çukurova University, Faculty of Medicine Department of Biochemistry, 01330, Adana
c
Ankara University,Engineering, Biomedical Faculty, Engineering Department,06100 Ankara
a
b
Hemoglobin (Hb) is a molecule that can act as a peroxidase in the presence of H2O2.
Recently, the spectrophotometric methods have been used to determine the peroxidase
activity of the hemoglobin molecule in human plasma fluid in the studies and Hb levels
have been reported with positive correlations.The immobilization studies of enzymes
onto support forstabilization,prolong the shelf life and resistance to harsh conditions
in sectors such as the food, medicine, medical, enzyme have been continued.In this
study, the immobilization of Hb on the solid support was investigated. The functional
and structural characterization of this material was performed. The effect of material
on endothelial cell superoxide dismutase (SOD) that is the antioxidant enzyme was
assayed. The Hbmolecules has been immobilized on tartaric acid-coated magnetic
nanoparticles, construction was analyzed by FT-IR, elemental analysis, SEM-EDX, XRD,
TEM spectrometry. Oxygen-carbon dioxide transportation capability of immobilized
Hb was investigated by CV.We can say that SOD antioxidant catalase activity did not
show a statistically significant difference compared to control (p> 0.05).These results
showed the natural conformation and function of hemoglobin are preserved. It is
suggested that obtained material isbiocompatible according to these results.
References:
[1]Kapralov A1, Vlasova II, Feng W, Maeda A, Walson K, Tyurin VA, Huang Z, Aneja RK,
Carcillo J, Bayir H, Kagan VE. Peroxidase activity of hemoglobin-haptoglobin complexes:
covalent aggregation and oxidative stress in plasma and macrophages. J Biol Chem. 2009 Oct
30;284(44):30395-407.
[2] Grigorieva DV1, Gorudko IV, Sokolov AV, Kosmachevskaya OV, Topunov AF, Buko IV,
Konstantinova EE, Cherenkevich SN, Panasenko OM. Measurement of plasma hemoglobin
peroxidase activity. Bull Exp Biol Med. 2013 May;155(1):118-21.
137
AMMONIA SYNTHESIS REACTION ON Ru NANOPARTICLES
M.Y.Aslan1, S. Akbayrak2, S. Özkar2, D. Üner1
1
Department of Chemical Engineering, Middle East Technical University, 06800 Ankara/Turkey
2
Department of Chemistry, Middle East Technical University, 06800 Ankara/Turkey
Our previous studies revealed that it is possible to synthesize ammonia at room
temperature using hydrogen spilled over on the support [1]. In the present study,
Ru(0)/zeolite-Y catalysts with different Ru loadings were prepared via ion exchange
method[2] to investigate the role of zeolite in accommodating spilled over hydrogen
and ammonia synthesis reaction under mild conditions. Ru(0)-zeolite-Y catalysts,
were characterized by H2 chemisorption, H2 and CO adsorption microcalorimetry. H2
chemisorption result of 2wt. % Ru(0)/zeolite-Y catalyst indicated high hydrogen uptakes
with very high initial heats of adsorption, confirming the small particles (in Figure 1).
Experiments are in progress demonstrating the role of zeolite and large number of
defect sites in N2 activation.
Figure 1: H2 microcalorimetry measurement of 2wt.% Ru(0)/Zeolite-Y
References:
[1] D. Uner and M.Y. Aslan, Using spilled over hydrogen in NH3 synthesis over supported Ru
catalysts, Catalysis Today (doi:10.1016/j.cattod.2015.11.038)
[2] M. Zahmakıran and S. Özkar, Langmuir, 25 (2009), 2667-2678
138
ARTIFICIAL HUMAN BLOOD and Antioxidant Enzyme Catalysis: Glutathione peroxidase, catalase
Ümit YAŞARa, Fatma ULUSALb, Bilgehan GÜZELb, Pınar Yılgör HURİc, Nurten DİKMENa
Çukurova University, Faculty of Medicine Department of Biochemistry, 01330, Adana
c
Ankara University, Engineering, Biomedical Faculty, Engineering Department,06100 Ankara
a
b
Artificial blood studiesbasically aims to improve the oxygen-carrying compound.The
main objective of this study will be blood substitute, which may carry blood and oxygen
absence lifesaving targeted promoter, it targeted improve biological material. The effect
of this solution on the enzyme activity that is antioxidant in vitro against the controls in
human endothelial cells was investigated.
Figure 1.Immobilization of hemoglobine
We immobilized ultra-pure hemoglobin molecule on the 3-(aminopropyl)
trimetoxysilan-glutalaldehyde coated magnetic nanoparticles using various techniques.
Construction was analyzed by FT-IR, elemental analysis, SEM-EDX, XRD, TEM
spectrometry. The effect of material on endothelial cell glutathione peroxidase (GPx)
and catalase (CAT) was assayed. Oxygen-carbon dioxide transportation capability
of immobilized Hb was investigated by CV. We can say that CAT and GPx activities
did not show a statistically significant difference compared to control (p> 0.05).These
results showed the natural conformation and function of hemoglobin are preserved. It
is suggested that obtained material isbiocompatible according to these results.
References:
[1]Kapralov A1, Vlasova II, Feng W, Maeda A, Walson K, Tyurin VA, Huang Z, Aneja RK,
Carcillo J, Bayir H, Kagan VE. Peroxidase activity of hemoglobin-haptoglobin complexes:
covalent aggregation and oxidative stress in plasma and macrophages. J Biol Chem. 2009 Oct
30;284(44):30395-407.
139
Ruthenium Nanoparticles Stabilized Hidrotalcite Catalyst for the
Methanolysis of Ammonia-Borane under Mild Conditions
Yaşar Karataş, a,b Ahmet Bulut,a Mehmet Yurderi,aMehmet Gülcan,a Mehmet
Zahmakıran,a,*
a
b
Muradiye Vocational School,Yüzüncü Yıl University, 65080, Van
Ruthenium(0) nanoparticles stabilized by hydrotalcite (HTaL) were prepared, for the
first time, by using a direct anionic exchange approach and subsequent reduction with
sodium borohydride at room temperature. The characterization of the resulting Ru@
HTaL material was done by using multi pronged analyses including ICP-OES, EA, P-XRD,
XPS,DR-UV–vis, BFTEM, HRTEM, STEM-EDX and N-adsorption–desorptiontechnique,
which revealed that the formation of ruthenium(0) nanoparticles (2.95 ± 0.9 nm)
stabilized by the hydrotalcite. The catalytic performance of Ru@HTaL interms of
activity, selectivity and stability was demonstrated in the methanolysis of ammoniaborane (NH3BH3) under mild conditions (at 25 .C). We found that Ru@HTaL catalyst
catalyzes the methanolysis of ammonia-borane at almost complete conversion (>
95%). Moreover, the resulting ruthenium nanoparticleswere found to be highly stable
against leaching and sintering, which makes Ru@HTaLa reusable heterogeneous catalyst
without losing of significant activity and selectivity.
140
Effect of Crystal Structure on the Catalytic Activity for SuzukiMiyaura Coupling Reaction
Fatma Ulusala,Burcu Darendelia, Özge Atışa, Mustafa Kemal Yılmazb, Bilgehan Güzela
a
b
Mersin University, Silifke Vocational College, 33343, MERSİN
The structure, geometry and surface morphology of the heterogeneous catalyst affect
the catalytic activity in the catalyst.This effect shows that it is possible to the selection
of the physical properties of the catalyst according to the desired product. Based on
this study, obtaining of desired geometry nanoparticles is gradually accelerated. It was
determined that catalytic activity is affected from the location of atoms in crystal lattice
and almost every atoms at different positions catalyzed different reactions.
Figure 1.Suzuki-Miyaura cross-coupling reaction results of various Pd(0) nanoparticles
In this study,the catalytic activity ofcarbon nanotube supported palladium
nanoparticles in Suzuki-Miyaura cross-coupling reaction was investigated. These
nanoparticles have various geometriesobtained by various deposition methods. Particle
sizes of nanoparticleswere selected approximately similar and for all of them the Pd/
substrate ratio was the same.InvestigatedPd(0) nanoparticles are in octahedral, cubic
and cuboctahedral geometry. Accordingly, while the cubic nanoparticles catalyzed
Suzuki-Miyaura reaction in a good yield,octahedral nanoparticles did not catalyze at all.
This study was supported by the Management Unit of Scientific Research Projects of
Çukurova University (BAP project no: FDK-2015-3668 under thesis).
References:
[1]Gillian Collins, Michael Schmidt, Colm O’Dwyer, Justin D. Holmes andGerard P.
McGlacken,Angew. Chem. Int. Ed., 53,2014, 4142 –4145.
141
Sulfonic Acid Functionalized MIL-101 Metal Organic Framework
Confined Palladium(0) Nanoparticles Catalyst for the
Methanolysis of Ammonia-Borane under Mild Conditions
Nurdan Caner,a Ahmet Bulut,a Mehmet Yurderi,a Mehmet Zahmakıran,a,
a
Palladium(0) nanoparticles stabilized by sulfonic acid functionalized metal-organic
framework (Pd@SMIL-101)were prepared, for the first time, by using a direct cationic
exchange approach and subsequent reduction with sodium borohydride at room
temperature. The characterization of the resulting Pd@S-MIL-101 material was done
by using multi pronged analyses including ICP-OES, EA, P-XRD, XPS,DR-UV–vis,
BFTEM, HRTEM, STEM-EDX and N-adsorption–desorption technique, which revealed
that the formation of palladium(0) nanoparticles (2.95 ± 0.9 nm) stabilized by the
framework of S-MIL-101by keeping the host framework intact (Pd@S-MIL-101). The
catalytic performance of Pd@S-MIL-101 interms of activity, selectivity and stability
was demonstrated in the methanolysis of ammonia-borane (NH3BH3) under mild
conditions (at 25 oC). We found that Pd@S-MIL-101 catalyst catalyzes the methanolysis
of ammonia-borane at almost complete conversion (> 95%). Moreover, the resulting
palladium nanoparticleswere found to be highly stable against leaching and sintering,
which makes Pd@S-MIL-101 reusable heterogeneous catalyst without losing of
significant activity and selectivity.
Figure 1: The network and pore structure of MIL-101metal-organic framework.
References:
[1] Ferey, G., Draznieks, C. M., Serre, C., Millange, F., Dutour, J., Surble, S., Margiloski, I. 2005.
“A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area”,
Science, 309, 2040-2042.
142
IMMOBILIZATION OF GLUTAMATE DEHYDROGENASE ONTO
AMINATED CARBON NANOTUBE AND INVESTIGATION OF CATALTIC
ACTIVITY
Yusuf Döğüşa, Gülüzar Özbolata, Hasan Ulusalb, Nevin Yılmaza, Abdullah Tulia
Cukurova University, Faculty of Medicine Department of Biochemistry, 01330 Adana, Turkey
Gaziantep University, Faculty of Medicine Department of Biochemistry, 27070 Gaziantep, Turkey
a
b
Enzymes which occuring within the cell, constitute life itself, regulate speed and
specificity of thousands of chemical reactions is very important for the body. As one of
the thousands of enzymes in our bodies can even lead to a fatal disease which shows us
how are they important. Such important structures to be stored in vitro environment
is quite important. Immobilized enzyme are becoming resistant to changes in ambient
conditions. And this allows that both conservation and use the enzyme in the more
temperate conditions. Enzyme immobilization has begun to attract increasing attention
since it has several advantages such as reusing enzyme, stabilization and long term use.
Carbon nanotubes, magnetic nanoparticles and support materials such as chitosan
are widely used in immobilization. Creation of appropriate groups are necessary
for immobilization of support material. Generally, intermediate arms which using
groups such as carboxylic acid and aldehyde are the most preferred materials in the
immobilization. In our study enzyme immobilization onto aminated carbon nanotubes
has been carried by means of glutaraldehyde intermediate arm.
In this study, glutamate dehydrogenase enzyme are bonded to aminated carbon
nanotube by forming imine bond with epichlorohydrin intermediate arm. The resulting
carbon nanotubes supported glutamate dehydrogenase enzyme activity was examined.
It was observed that there was improvement in shelf-life and storage conditions.
References:
[1]Atieh MA. Effect of Functionalize Carbon Nanotubes with Amine Functional Group on the
Mechanical and Thermal Properties of Styrene Butadiene Rubber. Journal of Thermoplastic
Composite Materials, 2011; 24- 613.
143
IMMOBILIZATION OF XANTHINE OXIDASE ONTO AMINATED
CARBON NANOTUBE AND INVESTIGATION OF CATALTIC ACTIVITY
AND STABILIZATION
Yusuf Döğüşa, Gülüzar Özbolata, Hasan Ulusalb, Nevin Yılmaza, Abdullah Tulia
a
b
Recently, enzyme immobilization has been begun to take place among the most
attractive subjects by the scientists. Immobilized enzyme are becoming resistant to
changes in ambient conditions. And this allows that both conservation and use the
enzyme in the more temperate conditions. Immobilized enzymes has advantages
such as resistance to high temperature and very low and high pH, long shelf life and
repeated use. Many support materials may be used for this purpose. Carbon nanotubes
constitutes a disadvantage in terms of the inability to digest by the body. But, the
functionalization of carbon nanotube by amination provides it to be biocompatible
and soluble. In this study, animated carbon nanotubes are bonded to enzymes by
means of glutaraldehyde intermediate arm. Change in stability were investigated by
examining the activity of obtained enzyme.
In this study, xanthine oxidase enzyme that catalyzes the last two stage of purine
degradation are bonded to aminated carbon nanotube by forming imine bond with
glutaraldehyde intermediate arm. The activity of obtained xanthine oxidase enzyme
which supported carbon nanotubes were examined. Besides activity, an increase in
stability has been observed.
References:
[1]Godber BL, Doel JJ, Durgan J, Eisenthal R, Harrison R. A newroutetoperoxynitrite: a role
forxanthineoxidoreductase. FEBS Lett. 2000; 475: 93–6.
[2]Atieh MA. Effect of Functionalize Carbon Nanotubes with Amine Functional Group on the
Mechanical and Thermal Properties of Styrene Butadiene Rubber. Journal of Thermoplastic
Composite Materials, 2011; 24- 613.
144
THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH
CAN BE USED FOR ACCUMULATION OF IRON IN THE BODY ON
GLUTATATHIONE PEROXIDASE ENZYME
Gülüzar Özbolata, Hasan Ulusalb , Yusuf Döğüşa, Abdullah Tulia
a
b
Glutathione peroxidase which is one of the most important antioxidant molecules
of intracellular medium is one of the most important enzymes which catalyse the
reduction of hydrogen peroxide and lipid peroxides. It is accepted that it provides an
efficient protection against lipid peroxidation. In this study, it is determined that the
degree of complexation of dimethylgloxime ligand which is considered for treatment of
excess iron occurs in the body, with the amount of lethal level of iron metal in water and
serum. The effect of ligand on activity and stability of glutathione peroxidase enzyme
was investigated to research using of ligand as a medicine.
Previously, dimethylgloxime ligand was used in many studies for different purposes in
the complexation of metals, but the therapeutic use of dimethylglioxime ligand for
iron accumulation in the body and the examination of its effect on enzyme activity are
investigated for the first time. In this study, Metal levels are reduced from lethal levels
to normal levels. Although promising results oriented using of dimethylglioxime with
enzyme studies as medicine are taken, more in vitro and in vivo studies are needed to
use dimethylglioxime as a medicine completely.
References:
[1] Anderson GJ. Mechanisms of iron loading and toxicity. Am J Hematol. 2007; 82:1128-31
[2] Day BJ. Catalase and glutathione peroxidase mimics, Biochem Pharmacol 2009; 77: 285-296.
145
THE INVESTIGATION OF DIMETHYGLOXIME LIGAND WHICH CAN BE
USED FOR ACCUMULATION OF IRON IN THE BODY ON XANTHINE
OXIDASE ENZYME
Gülüzar Özbolata, Hasan Ulusalb , Yusuf Döğüşa, Abdullah Tulia
a
b
Xanthine oxidase, has a key role in purine metabolism, is an important enzyme that
contains molybdenum. It has many biological functions such as regeneration of NAD,
iron absorption and mobilization and reduction of nitrates. In particular, synthesis
of uric acid which is final product of purine degradation are catalyzed by means of
xanthine oxidase enzyme. This important enzyme was chosen to investigate effect of
dimethylgloxime ligand, is thought to be used in the treatment of accumulation of iron
in the body, on enzyme activity.
In this study, it is determined that the degree of complexation of dimethylgloxime
ligand with iron molecule in serum and in buffer solutions at different pH. The effect of
ligand on activity and stability of xanthine oxidase enzyme was investigated to research
using of ligand as a medicine. Previously, dimethylgloxime ligand was used in many
studies for different purposes in the complexation of metals, but the therapeutic use of
dimethylglioxime ligand for iron accumulation in the body and the examination of its
effect on enzyme activity are investigated for the first time.
References
[1] Lavelli, V., Peri, C. and Rizzola, A. Antioxidant activity of tomato products as studied by model
reactions using Xanthine oxidase, Myeloperoxidase, and copperinduced lipid peroxidation. J.
Agric. Food Chem. 2000; 48(5); 1442-1448.
[2] Anderson GJ. Mechanisms of iron loading and toxicity. Am J Hematol. 2007; 82:1128-31
146
PREPARATION AND APPLICATION OF AlK(SO4)2.12H2O LOADED
CHITOSAN/ POLYVINYLPYRROLIDONE CATALYTIC MEMBRANE
Derya Unlua, Aynur Hacıoglua,Nilufer Durmaz Hilmioglua
Kocaeli University, Chemical Engineering Department, Engineering Faculty, Umuttepe, 41380,
Kocaeli
a
Ethyl acetate is one of the important solvents in the chemical industry. Ethyl acetate
has been used in the production of varnishes, plasticizers, synthetic resins and adhesives
[1]. Ethyl acetate is produced by esterification of acetic acid with ethanol [2]. These
reactions are usually catalyzed by homogeneous catalysts such as sulphuric or
p-toluenesulphonic acid. However, homogeneous catalysts have toxic and corrosive
properties and it is difficult to separate them from the reaction mixture [3].Therefore,
substitution of homogeneous catalyst by heterogeneous catalyst is very important
from the point of environment.The use of catalytic membranes as heterogeneous
catalysthas gained attention in recent years. In this study, Aluminum potassium sulfate
dodecahydrate loaded chitosan/polyvinylpyrrolidone (PVP) catalytic membranes were
prepared and used for synthesis of ethyl acetate. AlK(SO4)2.12H2O catalyst was added
to chitosan/PVP blend polymer solution and polymeric membrane solution with
catalyst was obtained. The membrane was prepared by solution casting method and
ready for usage after drying.Catalytic membranes cut into small pieces and added the
reaction mixture as the catalyst. Optimum reaction parameters (catalyst amount, initial
molar ratios (acid/alcohol), reaction temperature and reaction time) which were effect
the reaction yield were determined. AlK(SO4)2.12H2O loaded chitosan/PVP catalytic
membranes were found as efficient for synthesis of ethyl acetate.
References
[1] Otera J., Nishikido J., Esterification Methods, Reactions, and Applications, 2nd ed., Wiley,
Germany, 2010.
[2] Xia S., Dong X., Zhu Y., Wei W., Xiangli F., Jin W., Separation and Purification Technology,
2011, 77, 53–59.
[3] Hanumant G., Vijay V. B., Journal of Natural Gas Chemistry 19 (2010) 161–164.
147
PHOSPHOTUNGSTIC ACID LOADED CELLULOSE MEMBRANE
PREPARATION FOR CATALYTIC MEMBRANE REACTOR
Filiz Ugur Nigiza, Nilufer Durmaz Hilmioglua
a
Kocaeli University, Chemical Engineering Department, 41380, Kocaeli
Beside the process performance and reaction yield, it is also important to produce
the end product by using more effective input. Most of chemical reactions are carried
out by catalytically and catalyst consuming consists of non-ignorable part of the total
operation cost. Therefore, catalyst reuse and recycle become more important. Catalytic
membranes offer some advantages over the free catalysts such as easy processability.
It can be separated from the reaction media by simple separation techniques. Also
it can be used over and over without any activity loss. Either catalytic membrane
particles can be used as heterogeneous catalyst in a classical reactor or a catalytic
membrane module can be employed inside a reactor. For this purpose, homogeneous,
heterogeneous catalyst and lipases are distributed in a polymeric or inorganic matrix.
Recently, heteropoly acids (HPAs) loaded mixed matrix membranes have been used
owing to unique chemical, electronic properties and inherent catalytic activities [13]. In this study, phosphotungstic acid (PWA) filled carboxymethyl cellulose (CMC)
catalytic membrane was prepared by solution-casting method. The activity of catalytic
membrane was tested by producing ethyl lactate in a three-necked glass reactor. Effect
of temperature was investigated as function of lactic acid conversion. In Figure 1, PWA
particles were seen on the top surface of CMC matrix.
Figure 1. Surface SEM micrograph of catalytic membrane
148
References
[1] J.Pandey, A.Shukla, PVDF supported silica immobilized phosphotungstic acid membrane for
DMFC application, 262, 811–814.
[2] P.S. Rachipudi, A.A. Kittur, S.K. Choudhari, J.G. Varghese, M.Y. Kariduraganavar, Development
of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes
for dehydration of isopropanol, 45, 3116–3126.
[3] J. Pandey, F.Q. Mir, A. Shukla, Synthesis of silica immobilized phosphotungstic acid (Si-PWA)poly(vinyl alcohol) (PVA) composite ion-exchange membrane for direct methanol fuel cell, 39,
9473–9481.
149
Palladium(II)-Schiff base complex supported on mwcnt for using
as catalyst in the Suzuki-Miyaura reaction
Ayşen Berna Tekina, Bilgehan Güzela
a
Biaryl compounds play an important role in the biologically active substance and
synthesis engineering materials such as molecular wires, nonlinear optical devices and
liquid crystals. Suzuki-Miyaura cross coupling reaction is one of the most preferred
carbon-carbon bond-forming reaction for synthesis these compounds. Phosphine
ligands are generally heterogeneously or homogenously used in this kind of catalysis
reactions. The difficulty in synthesis, high cost, toxicity and low air and moisture
stability of phosphines are restrict the usability. Recently,metal complexes of various
ligand such asN-heterocyclic carbenes, Schiff bases and dendrimers have been used in
Suzuki-Miyaura reactions. These complexes have used as heterogeneously catalyst by
supporting on various inorganic and organic supports such as mesoporous silica, ionic
liquids, carbon nanotubes and polymersas well as homogenously using.
Figure 1.Preparation of MWCNT supported Schiff Base
In this work,palladium complex of Schiff Base-supported on multi walled carbon
nanotube (MWCNT)was synthesized and characterized. The catalytic activity and
reusability of synthesized complex was investigated heterogeneously in Suzuki-Miyaura
cross-coupling reaction was researched.
References:
[1]Mozhgan Navidi, Nasrin Rezaei, Barahman Movassagh, J. Organomet. Chem.,743, 2013, 63–69.
This study was supported by the Management Unit of Scientific Research Projects of Çukurova
University (BAP project no: FYL-2015-3633 under thesis).
150
Metal Organic Framework (MIL-101) Stabilized Ruthenium(0)
Nanoparticles: Highly Efficient Catalytic Material for the
Selective Hydrogenation of Phenol to Cyclohexanone
Ilknur Efecan Ertas, aMehmet Gulcan, aAhmet Bulut, aMehmet Yurderi,aMehmet
Zahmakirana*
a
Yüzüncü Yıl University, 65080, Van, Turkey
Ruthenium(0) nanoparticles stabilized by MIL-101 metal-organic framework (Ru/MIL101) were preparedvia gas phase infiltration of Ru(cod) (cot) (cod = 1,5-cyclooctadiene,
cot = 1,3,5-cyclooctatriene)followed by hydrogenolysis of Ru(cod) (cot)@MIL-101 at 3
bar H2 and 323 K. The resulting material was characterized by using various analytical
tools including ICP-OES, EA, P-XRD, XPS, DR-UV-VIS, SEM,BFTEM, HRTEM, STEMEDX,CO-chemisorption and N2-adsorptione desorption technique, which revealed that
the formation of ruthenium(0) nanoparticles (4.2 ± 1.2 nm) mainly exist on the surface
ofMIL-101 by keeping the host framework intact. The application of Ru/MIL-101 in
catalysis by consideringtheir activity, selectivity and reusability was demonstrated in the
phenol hydrogenation under mild conditions. Ru/MIL-101 acted as active (lower-limit
TOF = 29 mol cyclohexanone/mol Ru x h; correctedTOF = 88 mol cyclohexanone/
mol Ru x h at ≥ 90% conversion) and selective (≥ 90%) catalyst in the hydrogenation
of phenol to cyclohexanone in water at 323 K and 5 bar initial H2 pressure. More
importantly, the resulting ruthenium(0) nanoparticles in Ru/MIL-101 were found to
be highly durablethroughout the catalytic reuse in the phenol hydrogenation (retain
≥ 85% of their inherent activity andselectivity at 5th reuse), which makes Ru/MIL-101 a
reusable catalytic material for the liquid phasemediated catalytic transformations.
Figure 1: The network and pore structure of MIL-101metal-organic framework.
The financial support by the Scientific and Technological Research Council of Turkey
(TUBITAK, Project No: 113Z307) is gratefully acknowledged.
151
Trimetallic PdAuNi Alloy Nanoparticles Supported on
Amine Functionalized Reduced Graphene Oxide for the
Dehydrogenation of Formic Acid Under Mild Conditions
Mehmet Yurderia, Metin Çelebia, Ahmet Buluta, Mehmet Zahmakırana
a
Nanomaterials and Catalysis (NanoMatCat.) Research Group, Department of Chemistry, Faculty
of Science, Yüzüncü Yıl University, 65080, Van
Herein we report the development of a new highly active, selective and reusable
nanocatalyst; trimetallic PdAuNi alloy nanoparticles supported on amine-functionalized
reduced graphene oxide for additive-free dehydrogenation of formic acid (HCOOH),
which has great potential as a safe and convenient hydrogen carrier for fuel cells, under
mild conditions. This new catalytic material was characterized by the combination
of multi-pronged analytical techniques including ICP-OES, P-XRD, XPS, DR-UV/vis,
BFTEM, HRTEM, STEM-EDX, HAADF-STEM, FTIR and Raman spectroscopy.The sum
of their results indicative of the formation of trimetallic PdAuNİ alloy nanoparticles on
the surface of reduced graphene oxide at high dispersion.The catalytic performance
tests performed for the additive-free dehydrogenation of formic acid showed that our
new catalytic material acts as a highly active and selective heterogeneous catalyst for
this important catalytic transformation.
152
Synthesis and insitu catalytic aplication of 7-BER-NHC ligands
on Suzuki reaction
Sedat YAŞARªb, Emine Özge KARACAa, Nevin GÜRBÜZa,b,İsmail ÖZDEMİRa,b
b
ª Inönü University, Catalysis, Research and Application Center,44280, MALATYA, TURKEY
Inönü University, Faculty of Science and Art, Department of Chemistry, 44280, Malatya, TURKEY
Suzuki crosscoupling involves the reaction of an organo Halide with an organoborane,
which is an electrophile, to give the coupled product using a palladium catalyst and
base [1]. In order to reduce the generation of hazardous substances, variation in the
coupling reactions has been developed using green solvents, particularly water [2].
Biphasic catalysis is normally based on the conversion of known reactions from a onephase homogeneous system (solvent phase) to a two-phase homogeneous system
(water/solvent/reagents phases). Thecatalyst dissolved in the water phase could be
collected by decantation, extraction, or distillation. In such systems the advantages of
homogeneous and heterogeneous catalysis can be combined. Changing from volatile
organic solvents to water has enormous economic potential, avoids health risks,
and eases the separation of products from the catalyst. In these processes the water
solubility of the catalyst was increased via ligands with hydrophilic functionalities likeSO3-, -COO-, -OH, NR4+.
This study we study here the synthesis and characterization of new ring-expanded
NHC ligands. This ligands were tested as catalysts in the Suzuki coupling reactions of
arylchlorides in two-phase homogeneous system. These ligands exhibited moderate to
high catalytic activities under the given conditions.
References
[1] S. Yaşar, S. Çekirdek, İ. Özdemir, Heteroatom Chemistry, 25 ( 2014) 157.
[2] N. Gürbüz, E. Ö. Karaca, İ. Özdemir, B. Çetinkaya.,Turk. J. Chem., 39 (2015) 1115.
153
Improvement of Sulfur Regenaration Ability of NSR Catalysts via
Reducible Mixed Oxide Promoters
Z.Aybegum Samast, Emrah Ozensoy
Bilkent University, Chemistry Department, 06800, Ankara, Turkey
A common disadvantage of the NOx Storage Reduction (NSR) catalysts is the
deactivation and loss of NOx trapping ability due to sulfur poisoning [1].CeO2 promoted
catalysts can be used to enhance the regeneration ability of NSR systems due to their
favorable redox properties, high oxygen storage and transport capacity[2,3,4]. In order
toenhance thermal stability of ceria based systems; ZrO2 can be used as an additive.
Zhuet al. reported that incorporation of ZrO2 to Pt/CeO2 catalysts led to better DeNOx
catalytic performance [5].A recent study done by Jiang et al.revealed that Pt/Ba/
Al2O3/Ce0.6Zr0.4O2 has a highNSR performance, strong resistance against SO2 and good
regeneration ability [6]. In the current work, thermal sulfate/sulfite decomposition
(i.e. regeneration) capabilities ofvarious Pt/Ce/Zr/Ba/Al variants were compared via
in-situ FTIR and TPD. Pt10-10CeZrAl catalyst revealed complete thermal regeneration
surpassing that of a conventional Pt20BaAl commercial benchmark. Improvement of
the desulfationability via the addition of Ce/Zr mixed oxides to PtBaAl system can be
associated to the reversible redox chemistry of Ce/Zr oxides, enhanced Pt dispersion
and formation of novel Pt-O-Ce sites.
Figure 1.SOxdesorption via TPD for(a) Pt20BaOAl,(b)Pt10Ce-10ZrAl, (c) Pt10Ce10Zr8BaAl, and (d) Pt10Ce-10Zr20BaAl.Catalysts were initially exposed to 2.0 Torr SO2
+ O2 (g) mixture (SO2 : O2 = 1:10) at 673K and subsequently heated to 1100K in vacuum
during the TPD experiments.
References:
[1] S. Roy, A. Baiker, Chemical Reviews 109 (2009) 40-54.
[2] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Topics in Catalysis, 56 (2013) 950.
[3] Z. Say, E.I. Vovk, V.I. Bukhtiyarov, E. Ozensoy, Applied Catalysis B: Environmental 142, 143, 89
(2013).
154
[4]Kwak, J.H., Kim, D.H., Szanyi, J. and Peden, C.H.F.: 2008, Excellent sulfur resistance of Pt/BaO/
CeO2 lean NOx trap catalysts, Appl. Catal. B, 84, No. 3-4, 545–551.
[5] H. Zhu, J. Kim, S. Ihm, React. Kinet.Catal.Lett 97 (2009) 207.
[6] X.Wang, J.Mi, W. Wen, Z. Chen, L. Jiang, R. Wang, Materials Research Bulletin 75 (2016) 4146.
155
Selective CO2 adsorption studies on NaOH impregnated AC
Adsorbents
B. M. Eropaka, B. S. Çağlayanb, A. E. Aksoylua
Advanced Technologies R&D Center, Boğaziçi University, 34342 Bebek, Istanbul, Turkey
a
b
The combustion of fossil fuels is one of the major sources of the greenhouse gases,
especially CO2, which accounts for 40% of total CO2 emissions. It is crucial to develop
energy efficient CO2 capture (CC) technologies to reduce CO2 emissions and meet
the global demand of CO2 reduction. Selective CO2 adsorption has attracted great
interest, since it can be used in both pre-combustion and post-combustion technology
applications. In the current study, activated carbon (AC) based adsorbents, which have
advantages of large surface area and suitable porosity, were investigated in terms of their
CO2adsorption capacity, especially for CH4-CO2 feed mixtures. CO2 adsorption properties
can be enhanced by structural and chemical modifications applied on AC. Air or HNO3
oxidation procedures followed with NaOH impregnation, were applied. Selective
adsorption of CO2 from CO2-CH4 mixtures was studied on AC-based adsorbents with
different parameters, such as temperature, pressure, and adsorbate gas composition.
CO2 adsorption was found to be more favorable on NaOH impregnated AC-based
adsorbents than CH4 adsorption. It was observed that air oxidized AC adsorbents have
higher adsorption capacity than HNO3 oxidized AC adsorbents. NaOH impregnated
ACs were found to be promising adsorbents as they have high adsorption capacity
and selectivity towards CO2 adsorption. Increasing pressure leads a positive effect on
both CO2 and CH4 adsorption. Langmuir, Freundlich, and Dubinin Radushkevich(D-R)
isotherm models were investigatedon each experiment. ExplainingCO2 adsorption
behavior by Freundlich and D-R models was found to be convenient.
156
Spectroscopic Investigation of NOx Storage and Reduction
Pathways on Pt/K2O/ZrO2/TiO2/Al2O3 as NSR/LNT Catalysts
Merve Tohumeken, Zafer Say, Emrah Ozensoy
NOx Storage Reduction (NSR) materials have two major drawbacks namely, sulfur
poisoning [1] and thermal aging [2].Matsumoto et al. [3] reported that TiO2could be
used as a promoter against sulfur poisoning due to its high acidity. However, titania
can readily loseits functionality due to thermal deterioration at high temperatures[4].
In order to overcome this issue, ZrO2can beused together with TiO2in an attempt
to stabilize the titania component [5]. In this work, we analyzed NSR materials with
varying K2O loadingsin order to fine-tune the NOx storage capacity and NOxsurface
binding properties.NOxadsorption and desorption characteristics were investigated by
means of in-situ FTIR and TPD techniques. Figure 1 shows the in-situ FTIR spectra of
Pt functionalized ZrO2/TiO2/Al2O3(AZT) mixed oxides as a function of K2O loading in
the presence of NO2(g).NOx exposure on K2O-based materials yieldsvarious vibrational
features associated with monodentate surface nitrates on K2O and Al2O3(1510 and
1306 cm-1) and ionic/bulk like potassium nitrate (1392 and 1369 cm-1). Increase in K2O
loading leads to an increase in the formation of ionic/bulk like potassium nitrate and
suppression of surface nitrates. Moreover, the relative NOxstorage/releaseamounts
of these materials (obtained via TPD) can be ranked in the following order: Pt/10K/
AZT>Pt/5.4K/AZT>Pt/2.7K/AZT>Pt/AZT.
Figure 1. FTIR spectra showing the stepwise NOX adsorption on (a) Pt/AZT, (b) Pt/2.7K/AZT ,
157
(c) Pt/5.4K/AZT, (d) Pt/10K/AZT at 323 K.Red spectrum in each panel corresponds to the NOXsaturated surface(5.0 Torr NO2(g) for 10 min at 323K).
References:
[1] R. Hummatov, D. Toffoli, O. Gulseren, E. Ozensoy, H. Ustunel, J.Phys.Chem.C 116 (2012)
6191.
[2] S.M. Andonova, G.S. Senturk, E. Kayhan, E. Ozensoy, Journal of Physical Chem-istry C 113
(2009) 11014.
[3]S. Matsumoto, Y. Ikeda, H. Suzuki, M. Ogai, N. Miyoshi, Applied Catalysis B:Environmental 25
(2000) 115.
[4]S.M. Andonova, G.S. Senturk, E. Ozensoy, Journal of Physical Chemistry C 114(2010) 17003.
[5] K. Ito, S. Kakino, K. Ikeue, M. Machida, Applied Catalysis B: Environmental 74(2007) 137.
158
Removing of Synthetic Dyes from Aqueous Solutions By Using
Photocatalysis and Adsorption Methods
Ali Karaa, A.Çiğdem Karaerkekb
Chemistry Department, Uludağ Univ.,16285 Bursa, Turkey
Chemistry Department, Bursa Technical Univ., 16190, Bursa, Turkey
a
b
Synthetic dyes are mostly used in the textile, paper, plastics, leather and cosmetic industry
in recent times. Textile wastewater contain a large group of organic dye compounds that
causes serious threat to the environment owing to their non-biodegradability, toxicity
and potential carcinogenic risk. Several technologies such as adsorption, sedimentation,
filtration, photocatalytic degradation, etc. have been investigated and applied for dyes
treatment. Among these techniques, photocatalytic degradation of organic pollutants
under UV irradiation has received much attention for pollutants removal.Adsorption
method is one of the major traditional methods for the removal of synthetic dyes from
wastewater. Various inexpensive and efficient adsorbents have been developed for dye
adsorption. Recently, also photocatalytic degradation of organic pollutants under UV
irradiation has received much attention for pollutants removal.
In this work, we have synthesized a novel specific cross-linkedpolymer by suspension
polymerizationand characterized (FT-IR, SEM, H-NMR etc.). After characterization
studies, adsorption conditions for dyes are optimized at different parameters such as
pH and initial dye concentration. Polymers as adsorbents were applied to the removal
of sythetic dyes from aqueous solutions. Adsorption process was clarified by kinetic
and thermodynamic approachs.And than photocatalytic degradation of dyes were
investigated under photocatalytic conditions inaqueous solutions. Both of adsorption
and photocatalytic degradationefficiency were evaluated.
References:
[1] A.R. Khataee, M.B. Kasiri, Journal of Molecular Catalysis A: Chemical,Volume 328, Issues 1–2, 3
August (2010), Pages 8–26.
[2] Keith K.H.Choy, McKay G, Porter J F, Resources, Conservation and Recycling, 27, 1-2, (1999),
Pages 57-71.
[3] Kumar, M.N.V.R., Sridhari T.R., Bhavani K.D., Dutta P.K., Colorage 40, (1998), Pages 25-34.
[4] Ali Kara, Emel Demirbel, Nalan Tekin, Bilgen Osman, Necati Beşirli,Journal of Hazardous
Materials, Volume 286, 9 April (2015), Pages 612–623.
159
ANODIC BEHAVIOR OF CARBON SUPPORTED Ni-Co, Ni AND Co
ELECTROCATALYST IN DIRECT BOROHYDRIDE FUEL CELL
Alpay ŞAHİNa, İrfan ARb,
Gazi University, Faculty of Engineering, Department of Chemical Engineering, Ankara
a,b
Scope of this study is to synthesis catalyst for the direct borohydride fuel cell (DBHFC).
Synthesized anode catalyst must have the high thermal and mechanical stability,
suitable for the oxidation reaction of borohydride at anode and especially it has to
ability to prevent the hydrolysis. Direct borohydride fuel cells have received considerable
attention over the past decade due to their high power density and open circuit voltage,
high number of transferred electron and avoidance of CO poisoning of catalyst. In this
study, Ni/C, Co/CandNi–Co/C anode catalysts with remarkably high performance
were introduced to use in direct borohydride fuel cell (DBFC) andthey compared
with the conventional 10 wt% Pt/C anode catalyst. The structural and morphological
properties of the synthesized catalsyts were determined. In order to determine them,
Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and Fourier
Transform Infrared Spectroscopy (FT-IR) analyses were performed. After obtaining the
structural and morphological properties of the catalysts, thermo gravimetric analysis
(TGA) and thermal behavior of them were determined. After the characterization tests,
electrochemical tests like cyclic voltammetry (CV), chronopotentiometry (CP), linear
scan voltammetry (LSV) and in situ Fourier transform infrared (FTIR) spectroscopy
simultaneously with CV were done.The results indicated that the Ni–Co/C, Ni/C and
Co/C anode catalysts had higher activity compared to the 10 wt% Pt/C in borohydride
oxidation reaction (BOR).
References:
[1] Atwani M.H., Norhwood, D.O. 2007. “Evaluation of collidal Ag andA g-alloys as anode
electrocatalysts for direct borohydride fuel cells”, International Journal of Hydrogen Energy, 32,
3116-25.
[2] Duan, D., You, X., Liang, J., Liu, S., Wang, Y. 2015. “Carbon supported Cu-Pd nanoparticles as
anode catalyst for direct borohydride-hydrogen peroxide fuel cells”, Electrochimica Acta, 176,
1126-35.
[3] Li, S., Yang, X., Zhu, H., Wei, X., Liu, Y. 2013. “Ultrafine amorphous Co-W-B alloy as the anode
catalyst for a direct borohydride fuel cell”, International Journal of Hydrogen Energy, 38, 288488.
[4] San, F.G.B., Okur, O., Karadağ, Ç.İ., Isik-Gulsac, I., Okumuş, E. 2014. “Evaluation of operating
conditions on DBFC(direct borohyride fuel cell) performance with PtRu anode catalyst by
response surface method”, Energy, 71, 160-9.
[5] Yi, Lanhua., Wei, W., Zhao, C., Tian, L., Liui J., Wang, X. 2015. “Enhanced acitivity of AuFe/C anodic electrocatalyst for direct borohydride-hydrogen peroxide fuel cell”, Journal of Power
Sources, 285, 325-33.
160
THE POLYANILINE FILMS on ZnNi PLATED COPPER ELECTRODE
Nureddin Colak, A.Tuncay Ozyilmaz, Ibrahim Filazi
In industrial, metallic coatings such as zinc and nickel plating are among those most
widely used for protecting oxidizable metals in account of their high corrosion resistance
as well as good mechanical properties [1], [2]. The nickel plating and its alloying
component application in various industrial sectors including the automotive, electric
and electronic industry are insufficient to protect the oxidizable metals. So, polyaniline,
polypyrrole, polythiophen and their copolymers have attracted much interest for many
investigators [3], [4] and [5].
In this study, ZnNi coatings were successfully deposited on copper (Cu) applying current
of 2.5 mA with galvanostatic technique in 45 oC.ZnNi particles had homogenous,
smooth with light blue color. Polyaniline film (PANI), was covered with a dark greenbrown homopolymer film of strongly adherent homogeneous characteristic, was
synthesized with cyclic voltammetry technique from 0.10M aniline containing 0.20 M
sodium oxalate solution on zinc–nickel plated copper (Cu/ZnNi) electrode (Fig. 1).
Figure-1: Images of Cu (a), Cu/ZnNi (b) and CS/ZnNi/PANI electrodes, before (c) after (d) 360 h of
exposure time in 3.5 % NaCl solution
Corrosion performances of electrodes were evaluated using AC impedance
spectroscopy, anodic polarization curves and open circuit potential -time in 3.5 % NaCl
solution. The PANI homopolymer film provided an effective barrier property on zinc–
nickel coating due to this electrocatalytic behavior and a remarkable anodic protection
to substrate for longer exposure time.
References
[1] Lodhi, Z.F.S., Tichelaar, F.D., Kwakernaak, C.K., Mol, J.M.C., Terryn, H., de Wit, J.H.W., Sur.
Coat. Tech. 202 (2008) 2755
[2]Bajat, J.B., Maksimovic, M.D., Miskovic-Stankovic, V.B., Zec, S., J. Appl. Electrochem. 31 (2001)
355
[3] Tan, C.K., Blackwood, D.J., Corros. Sci. 45 (2003)545
[4] Ozyilmaz, A.T., Akdag, A., Karahan, I. H., Ozyilmaz G., Prog. Org. Coat. 76 (2013) 993.
[5] Ozyılmaz, A.T., Kardaş, G., Erbil, M., Yazici, B., Appl. Surf. Sci. 97 (2005) 242
161
Mn3O4 BASED ELECTROCATALYST SYNTHESIS FOR VANADIUM
REDOX FLOW BATTERIES
Büşranur DUMAN, Berker FIÇICILAR
Ondokuz Mayıs University, Department of Chemical Engineering Kurupelit Campus
Atakum,55139, Samsun
Electrical energy storageis a critical requirement for renewable energy systems such
as solar and wind energy for which energy is produced intermittently. Efficient energy
storage systems are needed so as to benefitoptimallyfrom solar and wind energy.In
the last two decades,flow batteries have made considerable progress and promising
efficiencies of these vanadium redox flow batteries (VRFB) systems made them to be
the pioneer in this field.
During the course of operation, two flow able electrolytes are circulated through
the anode and cathode side of the battery. Anode and cathode compartments are
separated by a proton conducting membrane. Both sides of the membrane are covered
with electrodes in which the half redox reactions take place. During the discharge of
the battery, anode goes under V+4/V+5 oxidation reactions, while the cathode electrode
goes under V+3/V+2 reduction reactions for the reversible VRFB cell. As electrons pass
through the external circuit, electricity is produced and protons are transferred from
anode to cathode side with the ion exchange membrane[1,2].
In thepresentstudy,major goal is to synthesize a suitable and durable electrocatalyst for
optimal operation of vanadium redox flow batteries. Instead of loading Mn3O4onto
graphite felt directly, we prefer to prepare electrodes by using hydrothermal method
in which solutions of manganese (II) acetate (Mn(CH3COO)2·4H2O) are used as
Mn3O4source. Consequently, graphite felt is placed within this solution to obtain the
working electrocatalyst. Finally, electrocatalyst loaded electrodes are characterized with
the aid of XRD, SEM, N2 adsorption instruments and the findings related to the electrical
and structural properties of the electrocatalysts will be presented in the conference.
References
[1]Rahman F., Skyllas-Kazacos M., Journal of Power Sources, 189 (2009),1212-1219.
[2]Kılavuz, K., 2011,Determınatıon Of Electrıcal Characterızatıon And Measurıng Performance Of
The Vanadıum Redox Flow Battery, Master thesis, İstanbul University, Energy Institute, İstanbul.
162
Synthesis, Characterization and Photocatalytic Performance of
Ag\ZnO in the Photodegradation of Methylene Blue under UV
Irradiation
Kadir KARAKAŞa, Metin ÇELEBİa, Mehmet ZAHMAKIRANa
a
Heterogeneous photocatalysis using novel functional materials could provide efficient
and important technologies for treatment of organic wastewater[1].Over the last
decade, ZnO with a wide band gap (Eg = 3.37 eV) is one of the most important
photocatalysts, which has been widely used in photocatalytic degradation of organic
pollutants[2]. Herein we report the preparation, characterization and the photocatalytic
use of silver nanoparticles supported on ZnO support material (Ag/ZnO). Ag/ZnO
was synthesized by wet-impregnation of PVP stabilized Ag(0) nanoparticles onto
ZnO surface followed by removing of surface bound PVP via heat treatment. The
resulting material was characterized by using various analytical tools, which showed
that formation of well-dispersed Ag(0) nanoparticles on ZnO support material. The
photocatalytic performance of Ag/ZnO was tested in the photodegradation of
methylene blue under UV irradiation. The results of these experiments have showed
that Ag/ZnO acts as highly active and reusable photocatalytic material for the
photodegradation of methylene blue.
Figure 1. BFTEM image of silver(0) nanoparticles supported on ZnO support material.
References:
[1] A. Akhundi, A. Habibi-Yangjeh, Ternary, Appl. Surf. Sci. 358 (2015) 261–269.
[2] M. Sun, T. Li, Z. Zhang, N. Wang, A. Xie, X. Lv, Y. Wang, F. Wu, M. Wang, RSC Adv. 5 (2015)
84406–84409.
163
SYNTHESIS OF CNT-TiO2-SiO2 NANOCOMPOSITE THIN FILMS: THE
EFFECT OF HEAT TREATMENT ON PHOTOCATALYTIC ACTIVITY
Tuğçe Kırbaş, Gürkan KARAKAŞ
Middle East Technical University, Chemical Engineering Department, 06800 Ankara
CNT-TiO2-SiO2 nanocomposites was synthesized by sol-gel process and the thin
films over glass substrates were fabricated by dip coating method. The effect of
CNT addition, heat treatment temperature and atmospheres on the structure and
photocatalytic properties was examined. Thin film samples were prepared with and
without carbon nanotubes and the heat treatment process was carried out at different
temperatures under air and nitrogen atmosphere. Characterization of the samples
was performed by thermal analysis, XRD, SEM&EDS, elemental carbon analysis, XPS
and UV-Vis spectroscopy. Thermal analysis indicated that the oxidation temperature
of carbon nanotubes was reduced by the TiO2-SiO2 matrix and the weight loss for
CNT- TiO2-SiO2 sample heat treated under nitrogen was same with the sample heat
treated under air. XRD studies showed that the presence of CNT and also increasing
heat treatment temperature improved the crystallinity. The SEM images revealed that
CNTs were successfully incorporated in thin film structure. XPS studies showed that
there were oxygen vacancies on the surface which are very effective for photocatalysis.
In addition, heat treatment under inert atmosphere caused the reduction of Ti(IV) to
Ti(III) on the surface. The photocatalytic activity tests were performed by monitoring
the degradation of methylene blue under UV irradiation in the presence of the thin
film. The CNT-added samples have higher photocatalytic activity than the TiO2-SiO2
sample. And also heat treatment temperature can favor the photocatalytic activity
until the sintering whereas the heat treatment atmosphere did not have a significant
effect on activity.
164
Determination of Reaction Kinetics for Electrochemical Oxidation
of Tetracycline Antibiotic using Boron-Doped Diamond Anode
Bahadır K. KÖRBAHTİ, Selin ALACA
Mersin University, Faculty of Engineering, Chemical Engineering Department, 33343, Çiftlikköy,
Mersin
In this study, electrochemical oxidation of tetracycline antibiotic was investigated using
boron-doped diamond (BDD) anode in a batch electrochemical reactor. Reaction
conditions were operated at 200-1000 mg/L initial tetracycline concentration, 0-8 g/L
supporting electrolyte (NaCl), 4-20 mA/cm2 current density, and 25-45°C reaction
temperature at 120 min reaction time. Tetracycline concentrations were determined
using Shimadzu Prominence LC-20AD HPLC system, and chemical oxygen demand
(COD) analyses were done using Merck Spectroquant COD cell test method.Process
optimization was accomplished through response surface methodology in CCD
designed experiments using Design-Expert 9.0 software in order to determine the
influence of independent factors on tetracycline removal and COD reduction along with
the experimental conditions. Optimized conditions under specified constraints were
obtained for the highest desirability at 618 mg/L initial tetracycline concentration, 3.6
g/L supporting electrolyte, 13.4 mA/cm2 current density, and 36°C reaction temperature.
In a batch electrochemical reactor, the reaction rate of tetracycline degradation was
expressed based on tetracycline concentration, and overall electrochemical conversion
rate of pollutants was expressed based on COD concentration. Reaction kinetics was
determined by the method of initial rates, and specific reaction rate constants (k) were
obtained using Arrhenius equation. Under response surface optimized conditions,
reaction kinetic parameters for electrochemical oxidation of tetracycline antibiotic using
boron-doped diamond anode were evaluated and outlined in Table 1. The activation
energy (Ea) depends on the nature of the reaction, and fast reactions generally have
small Ea values.
Table 1. Reaction kinetic parameters for electrochemical oxidation of tetracycline antibiotic using
boron-doped diamond anode
Acknowledgement
This project was supported by TÜBİTAK (The Scientific and Technological Research Council of
Turkey) with Grant No. 111M341.
165
166
THE ELECTROCATALYTIC BEHAVIOR OF COPOLYMER FILMS ON
ZnFeCo DEPOSITED CARBON STEEL ELECTRODE
A.Tuncay Ozyilmaza, Gul Ozyilmaza, İ.Hakkı Karahanb,
Mustafa Kemal University, Department of Chemistrya and Physicsb31000, Hatay
In recent years, electrochemically synthesized polymer films have attracted much
interest for the improvement of substrate corrosion resistance as new anticorrosion
technology [1]. In this study, Zinc-iron-cobalt (ZnFeCo) plating was successfully
deposited on carbon steel (CS) applying current of 3 mA with chronopotentiometry
technique in acidic solution. The poly(aniline-co-o-anisidine) films were deposited on
ZnFeCo plated carbon steel electrode. The synthesis processes of copolymer films were
carried out under cyclic voltammetry condition from different monomer concentration
(1:9, 5:5, 9:1) containing 0.20 M sodium tartrate solution. SEM images clearly show that
ZnFeCo plated carbon electrode was covered with different copolymer film structure
of strongly adherent homogeneous characteristic (Figure 1.).
Figure 1. SEM images of CS/ZnFeCo(a), CS/ZnFeCo/1PANI-co-9POA(b), CS/ZnFeCo/5PANI-co5POA (c) and CS/ZnFeCo/9PANI-co-1POA (d) electrodes.
Corrosion performances of copolymer film coated and uncoated CS/ZnFeCo
electrodes were evaluated using AC impedance spectroscopy, anodic polarization
curves and corrosion potential-time in 3.5 % NaCl solution.ZnFeCo plating on carbon
steel electrode exhibited anodic protective on CS electrode. Changes in resistance of
copolymer film coated electrodes were related to strong adsorption of copolymer films
on the CS/ZnFeCo surface which led to the formation of a protective oxide layer due
to their electrocatalytic behavior.
Acknowledgement
The research project was funded by Technical Research Council of Turkey (TUBITAK), Project No:
TBAG- (110T745)
References
[1] A.T. Ozyilmaz, A. Akdag, I. H. Karahan, G. Ozyilmaz, Prog. Org. Coat. 76, (2013) 993.
[2]C.K. Tan, D.J. Blackwood, Corros. Sci. 45, (2003) 545.
167
ELECTROCATALYTIC CONDUCTING POLYMER FILMS ON Zn
DEPOSITED CARBON STEEL ELECTRODE
A.Tuncay Ozyilmaza, Gul Ozyilmaza, İ.Hakkı Karahanb,
Mustafa Kemal University, Department of Chemistrya and Physicb, 31000 Hatay
In this study, Zn plating was successfully deposited on carbon steel (CS) applying
current of 4 mA with galvanostatic technique in acidic medium. Depending on
the method and condition of plating, different results of protection are obtained.
In order to suitable passivation of zinc plated carbon steel (CS/Zn), only anodic
polarization of Cs/Zn electrode is required to generate a suitable surface prior to the
electropolymerization process. Polypyrrole (PPy) and poly(N-methylpyrrole) (PNMP)
films were synthesized on CS/Zn in sodium oxalate medium. Homopolymer films were
achieved as homogenously and adherently as shown in SEM (Figure 1).
Corrosion performances of homopolymer film coated and uncoated Cu/Zn electrodes
were evaluated using AC impedance spectroscopy, anodic polarization curves and
open circuit potential -time in 3.5 % NaCl solution (Figure 2). The homopolymer films
which had electrocatalytic efficiency provided aneffective barrier property on zinc
coating and a remarkable anodic protection to substrate for longer exposure time.
Acknowledgement
The research project was funded by Technical Research Council of Turkey (TUBITAK), Project No:
TBAG- (110T745)
References
[1]J.B. Bajat, M.D. Maksimovic, V.B.M.-Stankovic, S.Zec, , J. Appl. Electrochem. 31, (2001), 355.
168
COBALT-BASED COORDINATION COMPOUNDS FOR
ELECTROCATALYTIC WATER OXIDATION
Emine Ülkera,b, Aysun Tekina, Satya Vijaya Kumar Nunea, Ferdi Karadaşa,
Department of Chemistry, Recep Tayyip Erdogan University, 53100Rize, Turkey
a
b
The development of alternative renewable energy sourceshas recently received
much attention due to limited suppliesof fossil based fuels and their damage to the
environment as a result of carbon emissions.[1].Hydrogen economy, which involves the
use of solar energy to split water to hydrogen and oxygen, has the potential to fulfill our
demanda clean and renewable energy source [2]. The main bottleneck in Hydrogen
Economy is considered to be oxygen evolution half-reaction since this four-electron
process requires high overpotentials. Efficient, stable, and cheap catalysts for water
oxidation are needed to overcome this problem [3].
It is aimed to useamorphous cobalt-based coordination compounds as water-oxidation
catalysts in this study. Synthesis and characterization of amorphous Co-Fe Prussian Blue
coordination compounds have beencarried out. Electrochemical and electrocatalytic
water oxidation studies have also been performed on samples deposited on FTO
electrode.
References
[1] A. Singh, L. Spiccia, Coordination Chemistry Reviews, 257 (2013) 2607– 2622.
[2] M.L. Wald, Scientific American ed., Guilford, USA, 2007.
[3] T. Kuwabara, B. Nishizawa, K. Nakamura, Y. Ikeda, T. Yamaguchi, K. Takahashi, Journal of
Electroanalytical
Chemistry, 740 (2015) 14–20
169
Determination of optimum Cu-CeO2 ANODE composition for
direct methane solid oxide fuel cell
Vedat Sarıboğaa, M.A. Faruk Öksüzömera
a
Solid oxide fuel cells (SOFCs) have a great attention in the last decades. Solid oxide fuel
cells work at high-temperatures (~800ºC), which provides advantages like using Pt-free
electrodes compatible with combined heat and power system and different types of
fuels[1,2].
Figure 1.Fracture cross-section SEM images of 30CeO2/70 Cu sample
In this work, the optimum compositions for Cu-CeO2-YSZ anode were introduced
as a solid oxide fuel cell anode structure. Minimum Cu content, suitable infiltration
technique and optimum CeO2 amounts were determined. Continuum percolation
limit of metallic Cu was demonstrated as %30 by mass in YSZ matrix. Simultaneous/
sequential impregnation of Cu and CeO2 salt solutions were investigated with XRD
and SEM techniques. It was concluded that the phase distribution in YSZ scaffold was
more efficient and no chemical interaction between Cu and CeO2 with co-calcination
process with simultaneous infiltration. The corresponding optimal Cu /CeO2 loading
was investigated with single cell I-V characterization and %35 Cu- %15 CeO2- %50 YSZ
cermet structure has been put forward as an ideal cell composition.
References
[1] A.B. Stambouli, E. Traversa, Renewable and Sustainable Energy Reviews, 6 (2002) 433.
[2] S. McIntosh, R.J. Gorte, Chemical Reviews, 104 (2004) 4845.
170
Characterization of PAni-Fe Electrocatalyst Loaded on Multiwalled Carbon Nanotube Support
Göknur Dönmeza, Merve Deniza, Hüseyin Deligöza,
Istanbul University,Faculty of Engineering, Department of Chemical Engineering, 34320, Avcılar,
İstanbul
a
Fuel cells are devices that convert the chemical energy of a fuel directly into electrical
energy in an electrochemical reaction. Fuel cells are popular among the alternative
energy sources because of their high efficiency, low working temperature depending
on the fuel type, fast response time, low mechanical parts, modularity and fuel diversity.
The oxygen reduction reaction is an important electrochemical reaction in the polymer
electrolyte membrane fuel cells. Because this reaction is critical for electrochemical energy
storage and conversion technologies. However, there is a restrictive parameter for using
the PEMFCs. ORR electrode kinetics are very slow at high over-potential. Consequently,
an efficient electrocatalyst is needed to accelerate the ORR kinetic. Platinum based
catalysts are very useful because of their activity and durability for ORR, also they are
very rare and expensive. Therefore, it has to be developed a new catalyst having high
activity, durability with cheapness for some technological device like PEMFCs [1]. This
research deals with the synthesis of electrocatalyst containing polyaniline. This nonprecious catalyst for ORR was synthesized by oxidative polymerization ofaniline on
the surface of multi-walled carbon nanotube in an aqueous medium in the presence
of iron salt. After polymerization, vacuum dried mixture was heat-treated at different
temperaturesunder an inert atmosphere for a known time. Then heat-treated sample
was leached with acid and washed with deionized water for removing unstable and
inactive species from the catalyst. Finally, the cathode catalyst was heat-treated again
[2, 3].
References
[1] Gang W., Zhongwei C., and Jiujun Z., Editors: San P. J., Pei K. S., CRC Press, Boca Raton, 2014.
[2] Zaiyong M., Hongliang P., Huagen L., Shijun L., Electrochimica Acta, 99 (2013) 30-37.
[3] Gang W., Karren L. M.,Christina M. J.,Piotr Z., Science,332 (2011) 443-447.
171
Benzene Oxidation as an Alternative Method for Assessing
Photocatalytic Activity
M.M. Oymaka, T. Tabarib D.Unerb
Hantek,Öveçler Mah. 1328. Cad., Çankaya Ankara, 06460, Turkey
Middle East Technical University Chemical Engineering Department, Ankara, 06531, Turkey
a
b
The standard method of assessing photocatalytic activity of the materials is NO oxidation
[1]. However, NOx analyzer is not a widely accessible instrument and as such simpler
assessment techniques are needed. In this study, we reportphotocataytic oxidation of
benzene as an alternative and complementary method to determine photocatalytic
activity. Benzene is chosen as a test material due to the its known stability to catalytic
reactions and photolysis reactions, especially at room temperature [2]. A batch reactor
system was used to determine benzene photo-oxidation over photocatalytic materials.
Baseline studies involved TiO2from different manufacturers and comparing the activity
with standard NO oxidation tests. The reactor system was described in detail elsewhere
[3]. The results revealed that benzene oxidationunder batch conditions can be used as
analternative method to determine the photocatalytic activity.
Figure 1.Comparison of NO and Benzene photocatalytic oxidation activity.using grout samples with
different TiO2%.
172
References
[1] ISO 22197-1:2007 e Fine ceramics (advanced ceramics, advanced technical ceramics) e Test
method for air-puri fi cation performance of semiconducting photocatalytic materials e Part 1:
Removal of nitric oxide; 2007.
[2]Zuo G-M., Cheng Z-X., Chen H., Li G-W., Miao T., J. Hazard. Mater.B128 (2006) 158.
[3]Oymak M.M., Photocatalytic Activity in Nano Sized Titanium Dioxide Structures, PhD Thesis,
Chemical Engineering Department, METU, Ankara (2012).
Pd-PEPPSI-Type N-Heterocyclic Carbene Complexes:
173
Synthesis, Characterization and Catalytic Activityin The Direct
Arylation Reactions
Murat Kaloğlua,b, İsmail Özdemira, Henri Doucetc, Christian Bruneauc
b
ª İnönü University, Catalysis Research and Application Center, 44280, Malatya / TURKEY
İnönü University,Faculty of Science and Arts,Chemistry Department, 44280, Malatya / TURKEY
c
Université de Rennes 1, Sciences Chimiques de Rennes, 35042, Rennes / FRANCE
N-Heterocyclic carbenes (NHCs) and their transition metal complexes have attracted
increasing attention in recent years, due to their wide applications in catalysis and
material sciences [1]. Numerous of NHC containing transition metal complexes
were developed until now, including metals such as Co, Pd, Cu and Ni. Among
them, complexes composed with NHCs and Pd constituted one of the prominent
representatives owing to their robustness against air, moisture and heat, which also
exhibited excellent catalytic activities in cross-coupling reactions [2,3].
Over the last twenty years Pd-PEPPSI-Type NHC complexes(PEPPSI= PyridineEnhanced Precatalyst Preparation Stabilization and Initiation) have gained real practical
importance in numerous catalytic processes, the most prominent application for such
ligands being their use in palladium-catalysed cross-coupling reactions.
In this study Pd-PEPPSI-type NHC complexes have been synthesised and have been
characterised by an X-Ray diffraction study. The catalytic properties of these palladium
complexes were evaluated in the direct arylation reactions of the heteroatomcontaining aromatic compound derivatives by using electron-deficient aryl halides as
coupling partners.
References:
[1] F. Bellina, Recent Developments in Pd-Catalyzed Direct Arylations of Heteroarenes with Aryl
Halides, Springer International Publishing, Switzerland, (2015).
[2] F. Zhu, Z. X. Wang, Organic Letters, 17 (2015) 1601-1604.
[3] H. Ren, Y. Xu, E. Jeanneau, I. Bonnamour, T. Tu, U. Darbost,Tetrahedron, 70 (2014) 28292837.
174
SYNTHESIS STUDIES OF THE PROMISING CATALIST; MIL-101
Emine EKİNCİ a
Gazi University, Engineering Faculty, Chemical Engineering Department, 06570,Maltepe- Ankara,
Turkey.
a
MIL-101 is a kind of Metal Organic Frameworks (MOFs), which have attracted much
attention in the past decade due to its promising application in chemical industries.
MIL-101 also known as “Porous Chromium Terephthalate”wasinitially synthesized by
“Material Institut Lavoisier”.It has very high surface area and pore volume. MIL-101
exhibits exceptional stability against moisture and other chemicals and is composed
of coordinately unsaturated Cr- sites with high concentration available for catalysis
and adsorption [1]. The surface area of MIL-101 can be greater than 4000 m2/g which,
however,isvery difficult to obtain due to the impurities coming from the synthesis
chemicals. The aim of the presented study is to developasynthesis procedure to
obtain MIL-101 crystalline structure with high surface are and pore volume. MIL-101
was synthesized by hydrothermal method andcharacterized by XRD, N2 adsorption
and desorption analyses (BET surface area, particle size, etc.), andSEM.XRD patterns
show the presence ofMIL-101’s crystal structure with high surface area (~2400 m2/g).
Adsorption-desorption isotherms indicated atype IV isotherm according to the
IUPAC classification of adsorption isotherms typical of mesoporous solids. According
to BJH pore size distribution homogeneous pore size distributions both in micro and
mesoporous zones were obtained.
Acknowledgements:
Financial support from University Research Funds through Gazi University (06/2015-09) is gratefully
acknowledged.
References:
[1] Henschel, A.,Gedrich, K., Kraehnert, R., Kaskel, S., Chem. Comm, (2008)4192-4194
175
Synthesis of Chiral Catalysts and Their Catalytic Activities in
ScCO2
Aysen DEMİR*, Burcu DARENDELİ, Bilgehan GÜZEL
Çukurova University, Faculty of Science and Letters, 01330 Adana, TURKEY
Enantiopure chiral complexes play a significant role in performing asymmetric synthesis
in homogeneous catalysis reactions. There is a lot of interesting about chiral binaphthyl
Schiff base complexes for using asymmetric reactions. [2,3] This type of catalytic
reactions showed high yield and selectivity with schiff base derivative metal complexes.
It is known that various metal complexes have been used widely in C-C coupling
reactions.
In this work,chrial schiff base ligands with perflourinated aldehydes and binaphthyl
amines will be synthesized (Figure 1.).Transition metal complexes of this ligand will
be prepared as catalysts and their catalytic activities will be performed in scCO2.
Effect of some parameters such as pressure, temperature and reaction timeon the
enantioselectivity of the synthesised catalyst will be investigated.
Figure 1. The structure of chiral binaphthyl Schiff base metal complexes
References:
[1]Pozzi G. , Shepperson I., Fluorous chiral ligands for novel catalytic systems, Coordination
Chemistry Reviews,242, 115-124, 2003.
[2] Kainz, S., Koch, D., Baumann,W. Ve Leıtner, W., Perfluoroalkyl –Substituted Arylphosphanes as
Ligands for Homogeneous Catalysis in Supercritical Carbon Dioxide. Angew. Chem. Int. Engl.,
36 (15) : 1628-1630, 1997
[3] Birdsall D. J.,Hope E. G., Stuart A. M., Chen W.,Hub Y., Xiao J.,Synthesis of fluoroalkylderivatised BINAP ligands,Tetrahedron Letters 42, 8551–8553, 2001.
176
GREEN DEHYDROGENATION OF DIMETHYLAMINE-BORANE
CATALYZED BY PVP, Al2O3AND PS-co-MASTABILIZED Ru NPs
BERİVAN BUKAN, Sibel DUMAN
Bingol University, Chemistry Department, 12000, Bingol
There are many methods for hydrogen obtained from dimethylamine-borane (DMAB)
used as the solid hydrogen storage materials. Generally, hydrogen is obtained from
DMAB activated by suitable catalysts in the solvent medium or thermally at high
temperatures[1, 2]. Although good results are also obtained with both approaches,
these methods are toxic, time consuming, costly and not atom-economic because in
these methods are used solvents that are expensive and pollution created or carried
out in unsuitable reaction temperature for practical applications. However, thanks
to solvent-free reaction applications (green synthesis) will not need to expensive and
environmental pollution created solvents and additional energy and cost for removal
of solvents, therefore environmental pollution will be prevented while both energy and
solvent savings will be provided[3,4].
Herein, DMAB that has low melting point (~35ºC) was used as reducing agent for
synthesis of Polyvinylpyrrolidone (PVP), Aluminum oxide (Al2O3) and Poly(styreneco-maleic anhydride (PS-co-MA)-stabilized Ru NPs. We report thatthese RuNPs are
normally obtained by decomposition of Ru(acac)3 during the solvent-free (green)
dehydrogenation of DMAB under inert gas atmosphere at nearly room temperature
(35+0.1°C).These Ru NPs were characterized HRTEM-EDX, SEM, XRD, XPS, NMR and
UV-Vis spectroscopy. The quantitative heterogeneity of the in situ generated these Ru
NPs in the green dehydrogenation of DMAB was identified by 1,10-phenanthroline
poisoning experiments. Also, the detailed kinetics in the green dehydrogenation
of DMAB was studied by varying catalyst and substrate loadings and temperature.
All results were compared with each other investigating by many parameters (ratio
of DMAB/catalyst, catalytic activity, temperature, time, %yield, activation energy,
reusability, TOF, particle size etc) in the synthesis of active these Ru NPs.
References
[] Barın E.Ü., Masjedi M., Özkar S., Materials, 8 (2015) 3155-3167.
[2] Duman S., Masjedi M., Özkar S., Journal of Molecular Catalysis A: Chemical, 411 (2016) 9-18.
[3] Kalidindi S.B., Sanyal U., Jagirdar B.R.,Inorganic Chemistry,49 (2010) 3965–3967.
[4] Demir H., Duman S.,International Journal of Hydrogen Energy, 40 (2015) 10063-10071.
177
Catalytic applications andsynthesis of Pd-PEPPSI
N- Heterocyclic Carbene Complexes
Nazan Kaloğlua, İsmail Özdemirb, Henri Doucetc, Christian Bruneauc
İnönü University, Pharmacy Faculty, 44280, Malatya / TURKEY
İnönü University, Catalysis Research and Application Center, 44280, Malatya / TURKEY
c
Université de Rennes 1, Sciences Chimiques de Rennes, 35042, Rennes / FRANCE
a
b
Intensive attention has been paid to the properties and application of N-heterocyclic
carbene (NHC) complexes of transition metals, and the pioneering work on the
coordination chemistry of NHC ligands was independently reported by Wanzlick
and Öfele in 1968 and Lappert and co-workers in the early 1970s[1]. The isolation of
free NHC and utilization of NHC complexes in catalysis stimulated the search further.
Among the NHCs reported, five-membered NHCs derived from imidazol-2-lidenes,
imidazolin-2-ylidenes, triazolylidenes, and thiazolylidenes (abbreviated as 5-NHC) have
been extensively studied [2].
Ohta and co-workers reported the direct 2- or 5-arylation of furans and thiophenes,
with aryl halides, in moderate to good yields by using [Pd(PPh3)4] as the catalyst [3].
Since then, the palladium-catalyzed direct arylation of heteroaryl derivatives with aryl
halides has proved to be a powerful method for the synthesis of a wide variety of
arylated heterocycles. Only a few examples of (NHC)Pd-catalyzed direct arylations of
heteroaromatics have been reported to date[4].
In this study Pd-PEPPSI type NHC complexes have been synthesised. The catalytic
properties of these palladium complexes were evaluated the direct Arylation of Furan,
Thiophene and Thiazole Derivatives.
References:
[1] (a) Cardin, D. J.; Çetinkaya, B.; Lappert, M. F.; Manojlov, L.; Muir, K. W. J. Chem. Soc., Chem.
Commun. (1971) 400−401. (b) Cardin, D. J.; Çetinkaya, B.; Lappert, M. F. Chem. Rev.
72(1972)545−574.
[2] Herrmann, W. A. Angew. Chem., Int. Ed. 41(2002)1290−1309.
[3] Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 107(2007)174−238.
[4] Özdemir, İ .; Gö k, Y.; Ö zeroğlu, Ö.; Kaloğlu, M.; Doucet, H.; Bruneau, C. Eur. J. Inorg. Chem.
12(2010) 1798−1805.
178
Synthesis of poly(cyclooctene) derivatives bearing imidazole
end group by ROMP Reactions
Gülşah ÇALIŞGAN, Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa
Hacettepe University, Chemistry Department, 06800, Beytepe-ANKARA
a
Ring opening metathesis polymerization is an efficient method, used in the
polymerization of strained cyclic olefins bearing functional groups [1]. One of the
disadvantages of these reactions that are catalyzed Ru, Mo and W based transition
metal catalysts, is the poisoning of the catalyst in the presence of imidazole and
pyridine functional groups. Up to date, various methods were developed for the to end
functionalize the ROMP polymers [2]. Although several ROMP polymers with various
functional groups were developed with these methods, there are no imidazole end
functionalized ROMP polymers were reported in literature up to date.
In this study, cyclooctene monomer were polymerized using Grubbs first generation
catalyst and methyloleate as chain transfer agent, and one end ester capped polymers
were obtained in high yields (Scheme 1). With the modification of ester end groups
with imidazole substituted primary amines in the presence of Ti(O-i-Pr)4 and Sn(Oct)2,
imidazole end-capped novel poly(cyclooctene) derivatives were observed. Temperature,
catalyst type and amount, ester/amine mol ratio and such parameters were evaluated
to determine the optimum reaction conditions.
Scheme 1.Synthesis of imidazole end functionalized ROMP polymers
References
[1] S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. Am. Chem. Soc., 114 (1992), 3974–5.
[2] A. E. Madkour, A. H. R. Koch, K. Lienkamp, G. N. Tew, Macromolecules, 43 (2010), 4557-61
179
Direct Arylation with Palladium-NHC Complexes
Emine Özge KARACA,a,bNevin GÜRBÜZ,a,bSedat YAŞAR,a,bİsmail ÖZDEMİRa,b
İnönü University, Catalysis Research and Application Center,44280, MALATYA
İnönü University, Faculty of Science and Arts, Department of Chemistry, 44280, MALATYA
a
b
In recent years, the transition-metal-catalyzed socalled direct arylation has
undergone rapid development, and itrepresents a viable alternative to traditional
cross-couplingreactions with organometallic reagents [1]. Direct arylationreactions
through cleavage of C−H bonds is considered as anenvironmentally and economically
more attractive strategy [2].Consequently, the procedure provides a valuable
andstraightforward technique for the synthesis of biaryls. Ohta and co-workers
reported the direct 2- or 5-arylation offurans and thiophenes, with aryl halides, in
moderate to goodyields by using [Pd(PPh3)4] as the catalyst. Since then, thepalladiumcatalyzed direct arylation of heteroaryl derivativeswith aryl halides has proved to be
a powerful method for the synthesis of a wide variety of arylated heterocycles. Only
a few examples of (NHC)Pd-catalyzed direct arylations ofheteroaromatics have been
reported to date [3].
The synthesis and characterization N-heterocycliccarbene palladium(II) complexes
synthesized and characterized. Pd(II) complexes were tested as catalysts in the direct
arylation of furans, thiophenes, and thiazoles, with various aryl bromides. These
complexes exhibited moderate to high catalyticactivities under the given conditions.
References
[1] M. He, J. F. Soulé, H. Doucet, Chem. Cat. Chem., 6(2014), 1824.
[2] M. Miura, T. Satoh, In Modern Arylation Methods; Ackermann, L., Ed.; Wiley-VCH: Weinheim,
2009; pp 335.
[3]E. Ö. Karaca, N. Gürbüz, İ. Özdemir, H. Doucet, O. Şahin, O. Büyükgüngür, B. Çetinkaya.
Organometallics 34(2015), 2487.
180
Magnetic Nanoparticle Supported Latent Ruthenium Metathesis
Catalysts for Olefin Metathesis Reactions
Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa,
a
In recent years, reusable catalysts are become one of the most popular topics in
catalytic chemistry. In this content magnetic nanoparticles were used as novel support
materials in the development of novel and environmental friendly catalytic procedures.
Ruthenium based olefin metathesis catalysts were supported on surface modified or
coated nano Fe2O3 and Fe3O4 materials. With this method, reusable and magnetically
separable novel and efficient ruthenium catalysts were developed.
Scheme 1. Magnetic nanoparticle supported Grubbs first and second generation catalysts
In this study, -Fe2O3 core with an average particle sizes of 20-40 nm were coated with
poly(N-vinylimidazole) [PVI]. Grubbs first and second generation catalysts were
supported on PVI coated magnetic nanoparticles (Scheme 1). The obtained ruthenium
complexes were characterized by TEM, XPS, FT-IR and ICP-MS methods. These
catalysts were activated by acid addition or sonification and ring opening metathesis
polymerization (ROMP) and ring closing metathesis (RCM) reactions were carried out
in a controlled manner. While polymers with molecular weights (Mn) between 100450 kDa were obtained in ROMP reactions, sterically hindered RCM products were
synthesized in high yields.
References
[1] C. Che, W. Li, S. Lin, J. Chen, J. Zheng, J. Wu, Q. Zheng, G. Zhang, Z. Yang, B. Jiang.Chem.
Commun., 2009, 5990–5992
[2] D. Wang, D. Astruc, Molecules, 19, 2014, 4635-4653
181
Modification of Functional Polyesters by Metathesis Reactions in
the Presence of Hoveyda-Grubbs Type Catalysts
Didem OKUR, Bengi Özgün ÖZTÜRKa, Solmaz KARABULUT ŞEHİTOĞLUa,
a
Polyesters are one of the most important polymeric materials that are frequently used
in daily life, industrial and high-tech applications [1]. With the variation of monomers
(diols, diamines, polyamines, etc.) a wide range of polyesters with different physical and
chemical properties can be synthesized. One strategy to modify polyesters bearing
unsaturated cyclic groups is to use olefin metathesis reactions [2].Olefin metathesis is an
efficient method that is used organic and polymer chemistry. Among these reactions,
strained cyclic olefins can be modified by using ring opening/cross-metathesis (ROM/
CM). With the adaptation of these reactions into the polymer chemistry, various
functional polymers can be efficiently synthesized.
Scheme 1.Sn(Oct)2 catalyzed polyesterification reactions and modification procedures
In this study, 5-norbornene-2-carboxylate and 1,6-hexanediol were polymerized in the
presence of Sn(Oct)2 and polyesters with molecular weights (Mn) varying between 2-10
kDa were obtained. These polymers were modified by ring opening-cross metathesis
reactions in the presence of methyl acrylate and various olefin derivatvies and HoveydaGrubbs second generation catalysts (Scheme 1). Obtained polymeric structures were
characterized by GPC, 1H, 13C NMR and DSC-TGA analysis.
References
[1] S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. Am. Chem. Soc., 114 (1992), 3974–5.
[2] N. Kolb, M. A. R. Meier, Eur. Polym. J., 49 (2013), 843-852
182
Synthesis of Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 Type
Nanocomposite Catalystsfor Vitamin K3 Synthesis
Serhan Uruş
Chemistry Department, Faculty of Science and Letters, Kahramanmaraş Sütçü İmam University,
46100, Kahramanmaraş¸ Turkey.
Research and Development Centre for University-Industry-Public Relations, Kahramanmaraş
Sütçü İmam University, 46100, Kahramanmaraş Turkey.
The synthesis of aminomethylphosphine-metal complexes have opened a new door
to the catalytic applications of organic compounds[1,2]. Magnetic Fe3O4nano-core was
synthesized using microwave power in 1h. Novel nano-composite supported;Fe3O4@
SiO2@RN(CH2PPh2)2PdCl2bis(diphenylphosphinomethyl)amino ligands and their
Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX,
TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as
heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,
4-naphthoquinone (Vitamin K3, menadione, 2MNQ) in the presence of hydrogen
peroxide. Selectivity reached about 55-60 % with a conversion of 90-96 % using the
nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes
were very active in three times in the catalytic recycling experiments in five catalytic
cycles.
Figure 1. Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 TypeAminomethylphosphine Complex and Its EDX
Spectrum.
*This study has been supported by Kahramanmaraş Sütçü İmam University (Project
No: 2013/6-33 M and 2015/2-13 YLS).
References:
[1] B. P., Esposito, , R. Najjar, Coord Chem Rev. 232 (2002) 137.
[2] S. Uruş, M. Keleş, O. Serindağ, J. Inorg. Organomet. Polym., 20 (2010) 152-160.
183
Modification of Poly(norbornenediester) Derivatives with Primary
and Secondary Amine Groups
Elif Ak, Elif Yakut, Bengi Özgün ÖZTÜRK, Solmaz KARABULUT ŞEHİTOĞLUa,
a
Ring opening metathesis polymerization (ROMP) is an efficient polymerization method
to produce polymeric materials with advanced structures [1]. With the invention of
ruthenium based Grubbs type catalysts that are tolerant to air and moisture, there
have been a tremendous increase in ROMP related applications [2]. Although a huge
progress was achieved in ROMP reactions, ruthenium based metathesis catalysts are
still not tolerant to some coordinating functional groups such as imidazoles. In order
to overcome these obstacles, we developed a novel method to obtain imidazole
substituted poly(norbornene) which cannot be synthesized directly by conventional
ROMP reactions.
Scheme 1. ROMP polymers bearing functional groups
In this study, 5-norbornene-2,3-dicarboxylate derivatives were polymerized via ROMP
in the presence of Grubbs third generation catalysts. These polymers were then
modified by different amine groups such as 1-(3-aminopropyl)imidazole, octyl amine
and diallylamines in the presence of Ti(O-i-Pr)4, Sn(Oct)2 and 1,5,7-triazabicyclo[4.4.0]
decene (Scheme 1). All polymers were characterized by means of GPC, FT-IR, 1H and
13
C NMR analysis.
References
[1]T.M. Trnka, R.H. Grubbs, AccChem Res, 34 (1) (2001), 18–29
[2] P. Schwab, R.H. Grubbs, J.W. Ziller, J Am Chem Soc, 118 (1) (1996), 100–110
184
Reusability of nano-12-tungstophosporic acid cesium salt in
alkylation of benzene with dec-1-ene reaction
Elif AKBAYa, Gülberk DEMİR
a
Anadolu University, Dept. of Chemical Engineering, Eskişehir, 26470, Turkey
Alkylation of aromatic hydrocarbons with olefins is an important industrial process
for the production of linear alkyl benzenes (LABs) which are the primary raw material
of LAB sulfonates, a surfactant detergent intermediate[1-4].In this study, Reusability of
nano 12-tungstophosphoric acid cesium salt in benzene alkylation with 1-decene in
liquid phase was studied.
Reusability of catalyst was investigated at 343 K 7.4/1 for 3 hr, in the presence of 0.9g
cat./10 ml dec-1-ene nano Cs-TPA catalyst for five cycles.. In the presence of used
catalyst after five cycles, conversion of dec-1-ene and selectivity of products decrease
only about 4 and 6.5 % respectively while selectivity of isomer increase about 35 %
compared with fresh catalyst. This attributes that nano Cs-TPA activity still proceed in
isomerization step while decrease in alkylation step depending on shrinking pore.
After five reused cycles, the used catalyst was also characterized by XRF, XRD,
N2adsorption/desorption isotherms, average pore diameter, pore volume and BET
surface area. Characterization results demonstrates that mesopore structure of nano
Cs-TPA is roughly retained after the reactions, although the decreasing in the surface
area and pore volume and pore diameter suggest that some organics stuffed the pores
were not to be insufficiently removed in regeneration step.
References:
[1] Y. Liu, L. Xu, B. Xu, Z.Li, L. Jia, W. Guo, J. Mol. Catal. A: Chem. 297 (2009) 86–92
[2] J.L. Berna, L. Cavalli, C. Renta, TensideSurfact Det. 32 (1995) 122.
[3] C. Perego. P. Ingallina. Catal. Today 73 (2002) 3-22.
[4] Z. Da. P. Magnoux. M. Guisnet, Catal. Lett. 61 (1999) 203-206.
185
Alumina Supported Mn-Ce Sorbents for High Temperature
Desulfurization of Hydrogen Rich Gas Mixtures
Melike Kucukera, Sena Yasyerlia, A. Derya Deniz Kaynarb
Gazi University,Chemical Engineering Dept., 06530, Ankara
b
VestelDefence Industry, 06830, Ankara
a
Hydrogen-rich gas mixtures derived from fossil fuel processes such as auto thermal
reforming (ATR), integrated gasification combined cycle (IGCC) system, contains
hydrogen sulfide. H2S should be safely removed from these gases at high temperatures
due to its corrosive and toxic nature. It also causes poisoning of thecatalysts in units such
as solid oxide fuel cells (SOFC). High temperature desulfurization is based on the reaction
between solid metal oxide sorbent and H2S gas. In this study, γ-Al2O3 pellet supported
Mn-Ce oxide sorbents containing 20 wt% metalwere prepared by wet (3Mn1Ce@
Al2O3-w; Mn/Ce:3/1) and dry (3Mn1Ce@Al2O3-d; Mn/Ce:3/1) impregnation methods.
BET surface areas of γ-Al2O3, 3Mn1Ce@Al2O3-w and 3Mn1Ce@Al2O3-d were found as
173, 139 ve 135 m2/g, respectively. In the XRD patterns of all alumina supported Mn-Ce
sorbents, the characteristic peaks of γ-Al2O3 and CeO2 were detected while there was no
peak corresponding to Mn or Mn oxides. In order to determine the distribution of Mn
and Ce in the synthesized sorbent, EDS analysis were performed at different locations of
the pellets.The values of Mn+Ce amount in the sorbents were changed in the range of
15-26 wt% for 3Mn1Ce@Al2O3-w and in the range of 18-31 wt% for 3Mn1Ce@Al2O3-d.
Desulfurization tests were carried out in fixed bed reactor system at 800oC using 1%
H2S in He. After desulfurization tests,the EDS analysis gavesulfur retention capacities
as 0.032 g S/ g sorbent ve 0.029 g S/g sorbent for 3Mn1Ce@Al2O3-wand 3Mn1Ce@
Al2O3-d, respectively. Sorbent utilization values based on MnS formation which is the
theoretical sulfur retention capacities, were determined as 40% for 3Mn1Ce@Al2O3-w
and 38% for 3Mn1Ce@Al2O3-d.
Acknowledgement
TUBITAK (Grant No:213M027) is gratefully acknowledged.
References
[1] P. R. Westmoreland and D. P. Harrison, Environ. Sci. Technol., 10(1976), 659–661.
[2] S. Yasyerli, Chem. Eng. Process. Process Intensif., 47(2008), 577–584.
[3] L. Espinosa-Alonso, K. P. De Jong, and B. M. Weckhuysen, J. Phys. Chem. C, 112(2008),
7201–7209.
186
Catalytic Wet Peroxide Oxidation of Bisphenol A in Water
Fatma TOMUL
Mehmet Akif Ersoy University, Faculty of Arts and Sciences, Department of Chemistry,
İstiklal Campüs, 15100, Burdur,
Bisphenol A (BFA), an endocrine disrupting compound (EDC), is considered to be one
of the most important pollutants due to its adverse effects even at low concentrations
[1].BPA is only partially removed by the conventional treatment methods employed in
wastewater treatment systems, it has recently been detected in natural water bodies,
in potable water resources, and in wastewater treatment plant effluents[2-3]. It is
therefore important that organic pollutants that bear a potential risk to human health
and the environment are removed during water supply and/or wastewater treatment.
In this respect, the complete removal of BPA from aqueous solutions is of significance.
Notably, satisfactory results are obtained in the removal of organic pollutants by
advanced oxidation methods (AOPs) because hydroxyl radicals are not selective and
have high oxidation capacity[4].
In this study, the removal of BPA by the catalytic wet peroxide oxidation method
(CWPO), which is an economical and environmentally friendly AOP, is investigated.
The oxidation studies were carried out using Cu-Ti-pillared bentonite, Ag-Ti-pillared
bentonite and Fe-Ti-pillared bentonitesamples as catalysts at the conditions of 20 ppm
BPA, H2O2/BPA=68, 25ºC, pH 4 and 5 g/L mcat for a reaction time of 60 minutes. By 30
minutes, values close to complete conversion were observed in two samples except
Ag-Ti-pillared bentonite. For the Ag-Ti-pillared bentonite, a BPA conversion rate of 87%
was achieved at the end of 60 minutes. Although values close to complete conversion
were achieved for BPA within short oxidation times, the conversion rates attained for
total organic carbon were rather low even after 240 minutes. However, CWPO results
showed that increasement of pH causes a increase the time of oxidation. On the other
hand, by the time catalyst and BPA concentration is increased, the time of oxidation is
decreased as well [5]
Acknowledgements
This work was supported by the Scientific Research Project Department of Mehmet Akif Ersoy
University (Project No: 0198-NAP-13).
References
[1]Y.-H. Kim, B. Lee, K.-H. Choo, S.-J. Choi, Microporous Mesoporous Materials, 138 (2011) 184190.
[2]D.P. Subagio, M. Srinivasan, M. Lim, T.-T. Lim, Applied Catalysis B: Environmental, 95 (2010)
414-422.
[3] C. Li, Z. Wang, Y.J. Yang, J. Liu, X. Mao, Y. Zhang, Chemosphere 125 (2015) 86–93.
[4]A. Cihanoglu, G. Gündüz, M. Dükkancı, Applied Catalysis B: Environmental, 165 (2015) 687699.
[5]F. Tomul, F.T. Başoğlu, H. Canbay, Applied Surface Science, 360 (2016) 579-593.
187
Graphene Supported Aminomethylphosphine-Pd(II) and Pt(II)
Complexes: Highly Efficient Catalysts on Vitamin K3 Synthesis
Serhan Uruş1,2*, Mahmut Çaylar2, İbrahim Karteri3
Chemistry Department, Faculty of Science and Letters, Kahramanmaraş Sütçü İmam University,
46100, Kahramanmaraş¸ Turkey
2
Sütçü İmam University, 46100, Kahramanmaraş Turkey
3
Materials Science and Engineering Department, Graduate School of Natural and Applied
Sciences¸ Sütçü İmam University, 46100, Kahramanmaraş¸ Turkey.
1
Novel graphene oxide (GO) supported bis(diphenylphosphinomethyl)amino [GO@
CHO-NHArN(CH2PPh2)2] type ligands and their Pd(II) and Pt(II) complexes have been
synthesized and characterized with FT-MIR/FAR, SEM, EDX, TEM, XRD, TGA and UVVisible techniques. Additionally, GO@CHO-NHArN(CH2PPh2)2MX2 (M: Pd(II) and
Pt(II)) type eight complexes were used as heterogeneous nano-catalysts in vitamin K3
(2-methyl-1,4-naphthoquinone) synthesis. Especially, graphene oxide-supported Pd(II)
complexes showed the best catalytic activities with high selectivities[1,2]. Conversions
and selectivities were about 95-99 % and 60-65 % respectively for GO supported-Pd(II)
complexes. It is obtained that the area ratio of the D and G peaks as GO sheets is ID/IG
= 1.19. The average grain size of the GO and GO-Pd(II) are determined as 18.02 nm and
46.06 nm from Scherrer’s equation, respectively. The band gap (Eg) values of the GO
based structures are analyzed and enhanced from 3.31 eV to 4.21 eV.
Figure 1. Fe3O4@SiO2@RN(CH2PPh2)2PdCl2 TypeAminomethylphosphine Complex
and Its EDX Spectrum.
*This study has been supported by Kahramanmaraş Sütçü İmam University (Project
No: 2013/6-33 M and 2015/2-13 YLS).
188
References:
[1] E. Shimanskaya, V. Doluda, M. Sulman, V. Matveeva, E. Sulman, Chem. Eng. J. 238 (2014) 206.
[2] S. Uruş, M. Keleş, O. Serindağ, J. Inorg. Organomet. Polym. 20 (2010) 152.
189
N-Alkylation Reaction with Functionalized Ionic Liquids
Nevin GÜRBÜZ,a,bEmine Özge KARACA,a,bSedat YAŞAR,a,b İsmail ÖZDEMİRa,b
a
b
The chemistry of imidazolium derivatives has a wide variety of applications: with many
anions their salts form ionic liquids (ILs) which are regarded as promising solvents for
different applications, due to their low volatility, non-flammability and good thermal
stability. From 1,3-dialkylimidazolium cations N-heterocyclic carbenes (NHCs) can
be derived by a single deprotonation [1]. These compounds are of high interest as
organocatalysts;4 furthermore NHCs as ligands in transition metal complexes were
shown to have excellent catalytic [2] and also medical [3] effects. Ionic liquids (ILs) are
a class of organic salts that are liquid at or near room temperature. They are generally
composed of a large asymmetric organic cation and either an organic or inorganic anion.
The application of ILs is also growing very rapidly in chemical reaction and catalysis [4].
In this study novel functionalized ionic liquids based on pyrimidinium cation are
synthesized and characterized by studying its 1H, 13Cand elemental analysis. These ionic
liquids have been reported as a highly efficient catalyst for N-alkylation reaction of
aniline with alkyl chloride. Pyrimidinium cation employed as solvent for N-alkylation
reaction of aniline and butyl chloride to form secondary amine without using transition
metal additives and co-solvent.
References
[1] H. Oldamur, G. Dirk, M. Klemens, S. Laszlo´, N. Balazs, V. Tamas, N. Laszlo´; New J. Chem.,
34(2010), 3004.
[2] R. H. Crabtree, Coord. Chem. Rev., 251(2007), 595.
[3] K. M. Hindi, M. J. Panzner, C. A. Tessier, A. L. Cannon, W. J. Youngs, Chem. Rev., 109(2009),
3859.
[4] S. Demir, Y. Damarhan, İ. Özdemir, J. Molecular Liquids 204 (2015) 210.
190
The Coupling Reaction With Aryl Grignard Reagents in the
Presence of Iron/NHC Catalyst
İsmail Özdemir,a,bSerpil Demir Düşünceli,a,b Nevin Gürbüza,b
a
b
Transition-metal-catalyzed cross-coupling is one of the mostpowerful tools in organic
synthesis [1]. After dormancy fordecades, iron has attracted renewed attention as a
practicalcoupling catalyst due to its economic and ecological advantagesover the other
rare metal catalysts [2,3].
Biaryls are important structural units for a wide range offunctional molecules, such
as chiral ligands and catalysts,drug intermediates, liquid crystals, physiologically
activenatural products, organic electronic materials, and functionalpolymers. Therefore
we report a simpleand highly selective biaryl synthesis based on iron catalyzedcrosscoupling of aryl chlorides with aryl Grignardreagents. The reactions are easilycarried out
with catalytic amounts of iron salt and N-heterocycliccarbene (NHC) ligands(Figure1).
Figure 1. Iron/NHC Catalyzed Biaryl Coupling Reaction
This work was financially supported by the Technological and Scientific Research Council of Turkey
TUBİTAK-BOSPHORUS (France) [113Z605].
References
[1] N. Miyaura, Cross-Coupling Reactions: A Practical Guide in Topics in Current Chemistry, ed. by
N.
Miyaura, Springer, Berlin, 2002, Vol. 219, pp. 1159
[2] E. Nakamura, N. Yoshikai, J. Org. Chem. 75 (2010) 6061-6067
[3] A. Fürstner, R. Martin, H. Krause, G. Seidel, R. Goddard, C. W. Lehmann, J. Am. Chem. Soc.
130 (2008)
8773-8787.
191
Palladium-NHC Complex Catalyzed Cross Coupling Reactions
Serpil Demir Düşüncelia, Rukiye Zengin Yamana,İsmail Özdemira
Inönü University, Catalysis Research and Application Centre, 44280 Malatya, Turkey
a
Palladium catalyzed carbon-carbon cross-coupling reactions exemplify one of the
important processes in organic chemistry [1]. The Heck [2] and Suzuki [3] reactions
are among the most widely used reactions for the formation of carbon-carbon bonds.
These reactions are generally catalyzed by Pd complexes with various ligands [4,5].
Therefore, we report here the synthesis and characterization of palladium complex
bearing N-heterocyclic carbene (NHC) ligand. We investigated the catalytic activity of
new Pd-NHC complexes for Mizoroki-Heck and Suzuki-Miyaura C-C coupling reactions
(Figure1).
Figure 1.Palladium-NHC Catalyzed Cross Coupling Reactions
References
[1] Yin, L.; Liebsher, J. Chem. Rev. 107 (2007) 133-173
[2] Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 100 (2000) 3009-3066
[3] Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 36 (1979) 3437-3440
[4] Kotha, S.; Lahiri, K.; Kashinath, D. Tetrahedron 58 (2002) 9633- 9695
[5] Herrmann, W. A.; Cornils, B. Angew. Chem., Int. Ed. 36 (1997) 1048-1067
192
PHOTOCATALYTIC WATER SPLITTING OVER Au/SrTiO3CATALYST
Ramazan Yıldırıma, Dilara Saadetnejadb
Boğaziçi University,Bebek, 34342, İstanbul
Boğaziçi University,Bebek, 34342, İstanbul
a
b
In this study, it’s aimed to produce hydrogen via photocatalytic water-splitting under
UV and visible light. Photocatalytic water splitting offers many potential advantages
over other solar hydrogen production methods such as reasonable efficiency, lower
cost, small volume reactors [1]. Photocatalytic water splitting occurs on the surface
of photocatalyst which is at the heart of photocatalytic water splitting technology;
therefore new materials have been tried to be improved. Among them, several oxide
photocatalysts have been widely studied and most of the active materials are found to
be perovskite types [2]. By doping perovskites with plasmonic metals such as Au, Ag
and Cu, which are excellent cocatalysts that can promote visible light absorption, high
photocatalytic efficiency can be obtained. Recent studies show that plasmonic metals
on semiconductor such as TiO2, Bi2WO6 and La2Ti2O7 etc. enable to prevent charge
recombination and make light absorption higher [3].
In this work, semiconductor-based photocatalytic water splitting was done with
Au doped SrTiO3(perovskite) photocatalyst; Au dopping wereperformed using
homogenous deposition-precipitation method. A batch reactor was designed with a
homogeneous and efficient light-irradation quartz window. Both UV and visible ligh
sources were utilized. The results were analyzed using Gas chromatography.
References
[1] Liao C., Huang C., Wu J., Hydrogen Production from Semiconductor-based Photocatalysis via
Water Splitting, Catalysts, 2 (2012) 490-516.
[2] Ikada S., Fubuki M., Takahara Y., Matsumura M., Photocatalytic of hydrothermally synthesized
tantalate pyrochlores for overall water splitting , Applied Catalysis A General : 300 (2006), 186190.
[3] Bi J., Fang W., Li L., Li X., Liu M., Liang S., Zhang Z., He Y., Lin H., Wu L., Liu S., Wong P.,
Ternary reduced-graphene-oxide/Bi2MoO6/Au nanocomposites with enhanced photocatalytic
activity under visible light, Journal of Alloys and Compounds 649 (2015), 28-34.
193
IN SITU GENERATION COPPER(0) NPs AND CONCOMITANT GREEN
DEHYDROGENATION OF DIMETHYLAMINE-BORANE
Sibel DUMAN
Bingol University,Chemistry Department, 12000, Bingol
Use of catalysts that located in the 12 principles of Green Chemistry is an important
area of research. Application and investigation of catalysts how are non-perishable after
use, non-toxic, easily separated and reusable after reaction can be considered one of
the vital areas for the chemical industry [1]. Because of the relatively high use of oil
derivatives many chemical industry attempts to produce solvents with high E-factor
[2,3]. In addition to supercritical fluids, ionic liquids and fluorinated solvents produced
and used for this purpose, “The best solvent is no solvent” approach has been the focus
of our attention in this project [4,5].
In this study, dimethylamine-borane (DMAB) which has low melting point (35°C)
was used as both stabilizing and reducing agent while copper(0) nanoparticles
(NPs) were used as the active catalyst in the solvent-free (green) dehydrogenation of
DMAB. Catalytic activity of in situ generated copper(0) nanoparticles by stabilizing
cyclic bis(dimethylamino) borane, (Me2N)2BH, obtained as a result of interaction
of Cu(acac)2 and melted DMAB at nearly room temperature(30°C) in solvent-free
medium was examined and activation energy, Ea, was determined as 18 + 2 kjmol-1.
Average particle size of reusable, relatively inexpensive, active and stable copper(0)
nanoparticles was calculated from TEM images as 2,9 + 0,2 nm. It was clearly observed
that the resulting copper(0) nanoparticles were provided 200 total turnovers
over 50 h with an initial turnover frequency (TOF) value of 19 h−1 at nearly room
temperature with the generation of 1,0 equiv H2 at the almost complete conversion
of dimethylamine borane to cylic dimethylamino borane, [Me2NBH2]n units. These
nanoparticles obtained under solvent-free medium were charactarized by TEM, EDX,
HRTEM, P-XRD, 11B{1 H}-NMR, ATR-IR and UV-Vistechniques.
References
[]Paluri S.L.A., Edwards M.L., Lam, N.H., Williams, E.M., Meyerhoefer A., Sizemore, I.E.P. Journal
of Chemical Education, 92 (2015) 350-354..
[2] Quinones L., Grazul J., Martinez-Inesta M.M.,Materials Letters, 63 (2009) 2684-2686.
[3] Dahl J.A., Maddux B.L.S., Hutchison J.E.,Chemical Reviews,, 107 (2007) 2228-2269.
[4] Kalidindi S.B., Sanyal U., Jagirdar B.R.,Inorganic Chemistry,49 (2010) 3965–3967.
[5] Demir H., Duman S.,International Journal of Hydrogen Energy, 40 (2015) 10063-10071.
194
Synthesis of Palladium(II) Schiff Base Complex And it’s Catalytic
Activities C-C Coupling Reactions
Sinan SEVEN, Figen KOÇAK, Bilgehan GÜZEL
Çukurova University, Faculty of Science and Letters, 01330 Adana, TURKEY
The ligand assisted palladium (Pd)-catalyzed Suzuki–Miyaura cross-coupling reaction
is one of the most attractive methods in organic chemistry and phosphines have been
established as the best ligand system for this transformation. However, these phosphines
have significant limitations, such as;high toxicity and sensitivity to air. Recently, Schiff
bases have been recognized as excellent alternatives to phosphines in Suzuki–Miyaura
reactions [1,2].
This work has been included; the synthesis of Schiff base ligand by condensation of
4-fluoromethyl aniline with 2-hydroxy- 5-methyl benzaldehyde and its palladium
complex. All of the synthesized molecules were characterized by elemental analysis, FTIR, 1H NMR, 13C NMR. This palladium complex was used as catalyst for suzuki-miyaura
cross-coupling reaction over phenyl boronic acid and bromobenzene (Figure 1.)
Figure 1. The mechanism of Suzuki-Miyaura
References:
[1] P. Das, W. Linert, “Schiffbase-derivedhomogeneousandheterogeneouspalladiumcatalystsforthe
Suzuki–Miyaurareaction” CoordinationChemistryReviews, 311, (2016), 1-23
[2] Knozinger. H. “Heterogeneous Catalysis and Solid Catalysts” Ulmann’s Encyclopedia Of
Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA. (2003)
195
HYDROBENZOIN TYPE LIGANDS FOR ASYMMETRIC CATALYSIS
Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT,Yaşar GÖK*
Department of Chemistry, Faculty of Arts and Sciences, OsmaniyeKorkut Ata University,80000
Osmaniye, Turkey.
Asymmetric catalysis has become a growing field of study as the demand for more
enantiomerically pure compounds arises. Asymmetric catalysis requires that a chiral
catalyst be used in order to transfer its chirality to the substrate. An effective asymmetric
catalyst will quickly produce a chiral product in good yield with high enantiomeric
purity of the desired enantiomer[1].The discovery of new chiral auxiliaries or ligands for
catalysis continues to broaden the scope of many asymmetric processes.In this study,
chiral ligands, derived from C2-symmetric (R, R)-hidrobenzoin skeleton were synthesized
and applied as catalysts in different enantioselective reactions[2].
References:
[1] Ghent, B. L., Martinak, S. L., Sites, L. A., Golen, J. A., Rheingold, A. L., Nataro, C. J.
Organomet. Chem., 692 (2007), 2365-2374.
[2](a) Gök, Y., Kekeç, L. Tetrahedron Lett.55(2014),2727-2729.(b) Gök, Y., Küloğlu, S., Gök, H.Z.,
Kekeç, L. Applied Organometallic Chem.28 (2014) 835-838. (c) Gök, Y., Gök, H. Z. Helv.
Chim. Acta 98(2015) 490-495.
196
THE SYNTHESIS OF MAGNETIC NANOPARTICLES SUPPORTED
AZOMETHINE-OXIME-PD COMPLEX AND ITS CATALYTIC ACTIVITY
Eylül Büşra Hereytania, Fatma Ulusala, Bilgehan Güzela
a
Metal nanoparticles are used extensively as catalysts for a wide variety of reactions.
Among these catalysts, supported Pd catalysts are commonly used for hydrogenation,
oxidation, Heck and Suzuki-Miyaura cross-coupling reactions. Various materials such as
alumina, silica gel, magnetic nanoparticles, activated carbon, carbon nanotube, polymers
are used as support materials for these catalyst. Magnetic nanoparticlesare prefered due
to easy separable after using by magnet from reaction medium and forming the desired
functional groups of the ligands.
Figure 1.Preparation of catalyst
In this work, bifunctional Schiff Base-vic-dioxime ligand was synthesized and bonded via
oxime group to magnetic nanoparticles (Figure 1.). Pd complex of this MNP supported
ligand was synthesized and characterized by XRD, SEM, FT-IR, elemental analysis.
Synthesized magnetic complex was used in transfer hydrogenation reaction of styrene.
We present the first synthesized of magnetic nanoparticles supported bifunctional
Schiff Base-vic-dioxime ligand and Pd complex.
References:
[1] A. Kakanejadifard, Farnia, S. Morteza and Najafi, Golamreza Iran. J. Chem. & Chem. Eng., 23
(2004) 117-118.
[2] W.Ungnadel, Narath, And D. Barham, The Journal Of Organic Chemistry 28 (1962) 134-136.
197
N-Substitutedbenzimidazole-Ruthenium(II) Complexes and
Their Catalytic Activity
Kenan Buldurun,a Nevin Gürbüz,b,c İsmail Özdemirb,c
a
Muş Alparslan University, Faculty of Science and Arts, Departmant of Chemistry, 49250-MUŞ
a
b
The chemistry of azo-ligands have attracted considerable of attention because of the
interesting physical, chemical, photophysical and photochemical, catalytic properties
particulary in the low valent transition metal coordination and organometallic
compounds [1]. The Ru(II) complexes with ligands bearing N-donor atoms are attracting
interest of researchers due to their potential to promote the catalytic reaction of
organic compounds. For several reasons, nitrogen-containing ligands have been found
to be among the most convenient and attractive ligands for ruthenium complexes
[2,3]. A large number of ruthenium complexes with arene ligands have been employed
in different catalytic reactions including allylic alkylation, amination, cyclization,
cycloisomerization of dienes and hydroformylation and transfer hydrogenation [4,5].
In this study, N-coordinated 5-nitrobenzimidazole ruthenium(II)complexes
were synthesized by the reaction of [RuCl2(p-cymene)]2 with N-substituted
5-nitrobenzimidazole. These complexes that prepared and characterized has used as
catalyst in hydrogen transfer reaction.
Reference
[1]. M.S. Jana, A. K. Pramanik, S. Kundu, D. Sarkar, S. Jana, T. K. Monda, InorgChimActa, 394
(2013) 583–590.
[2]. D. Mercan, S. Dayan, N. Kayacı, N.O. Kalaycioglu, O. Dayan, E.Ç. Öztürk, InorgChimActa,
400 (2013) 74–81.
[3]. L. Gök, H. Türkmen, Tetrahedron 69 (2013) 10669-10674.
[4]. B. Çetinkaya, İ. Özdemir, C. Bruneau, P.H. Dixneuf, Eur. J. Inorg. Chem, (2000) 29-32.
[5]. D. Pandiarajan, R. Ramesh, J Org Chem, 723 (2013) 26-35.
198
Determination of Radiation Absorption Properties of Gamma
Irradiated Polyoxovanadate Based Catalysts
A.Çiğdem Karaerkeka, Faruk Demirb, Ali Karac
Chemistry Department, Bursa Technical Univ., 16190, Bursa, Turkey
Metall. and Materials Engineering Department, Bursa Technical Univ.,16190, Bursa, Turkey
c
Chemistry Department, Uludağ Univ.,16285 Bursa, Turkey
a
b
Determination of the mass attenuation coefficient μ/ρ, and the effective electron
number Neff, the effective atomic number Zeff, is very important in the fields of, radiation
protection, nuclear diagnostics, radiation dosimetry, nuclear medicine. μ/ρ, Neff and
Zeff, represent radiation interaction with materials. Zeff is one of the most convenient
parameter and represents characteristics of a multi element material especially in the
radiation field depending on atomic numbers of the constituent elements and incident
radiation energy. Recently, researchers have made extensive effective atomic numbers
studies on a variety of materials such as dosimetric materials, alloys, semiconductors,
building materials, glasses, soils, amino acids, minerals, and biological samples and
polymers. γ-ray irradiation changes the concentration of catalytically active sites
and alters the reducibility of the catalysts. Effect of such irradiations on the catalytic
properties of several compounds has recently been described for the different reactions.
In the literature it is described that the effect of varying doses of gamma ray irradiation
of novel polyoxovanadate based material on its catalytic performance for the oxidative
dehydrogenation of propane has been studied. In this work, we have computed
theoretical values of µ/ρ, Zeff and Neff of the polyoxovanadate compounds by using the
Direct- Zeff software program in different energy regions.
References:
[1] Adem Ün, Tanfer Caner, Annals of Nuclear Energy, Volume 65, March (2014), Pages 158–165
[2] Adem Ün, Faruk Demir, Applied Radiation and Isotopes,Volume 80, October (2013), Pages
73–77
[3] Hine, Phys. Rev., 85, (1952), pp. 725–737.
[4] M.Ishaque Khan, Kadir Aydemir, M.Rafiq H.Siddiqui, Abdulrahman A. Alwarthan, James A.
Kaduk, Christopher L.Marshall, Radiation Physics and Chemistry 88 (2013) 56–59.
[5] N. G. Kostova*, A. A. Spojakina,Journal of Optoelectronics and Advanced Materials, Vol. 7, No.
3, June (2005), p. 1347 – 1352.
199
EFFECTS OF THE PREPARATION METHOD AND CALCINATION
TEMPERATURE ON THE CHARACTERISTIC PROPERTIES OF NiOFe2O3-SiO2 CATALYSTS
Filiz BALIKÇI DEREKAYAa
a
Gazi University, Graduate School of Natural And Applied Sciences, Advanced Technologies
Department, 06500, Teknikokullar, Ankara, TURKEY
In this study the NiO-Fe2O3-SiO2 catalysts were prepared by using two different methods
which are co-precipitation and surfactant assisted co-precipitation method. All prepared
catalysts were calcined at two different temperatures which are 500oCand 700oC.
Catalysts were characterized by using different techniques which are N2physisorption,
x-ray diffraction and scanning electron microscopy (SEM-EDX). Multipoint BET surface
area results indicate that surface areas of the catalysts decreased by increasingthe
calcination temperature as a result of increase in average pore diameter which might
be due to the pore degradation to form big pores. Using of surfactant at preparation
has not good effect on the surface areas of the catalysts since catalysts prepared by the
co-precipitation method have higher surface area values. The Fe2O3 has positive effect
on the surface area of the catalysts that prepared by the co-precipitation method and
calcined at 500oC. Results indicate that 700oC calcination temperature is not convenient
in comparison with the 500oC. According to the x-ray diffraction studies the crystal
phases obtained from the catalysts calcined at 500oC are NiO, Fe2O3 and SiO2. The NiO
peaks observed at 2q=37°, 43°, 63° and 75°; the Fe2O3 peaks observed at 2q= 35° and
SiO2 peaks observed at 43° and 36.5° [1]. The broader peak of SiO2 which is at 2q=23°
was not observed. Wang Y. et.al. [2] and Wang W. et.al. [3] did not see this peak at their
studies over the Ni/SiO2 and Ni-Fe-SiO2 catalysts, respectively.
References:
[1] Dopminguez I., Barrio I., Catalysis Today, 133-135 (2008) 467-474.
[2] Wang Y., Li F., Cheng H., Fan L., 41 (8) (2013) 972-977.
[3] Wang W., Wang H., Yang Y., Jiang S., International Journal of Hyrogen Energy, 37 (11)(2012)
9058-9066.
200
Modular Ligands Allowing Tunable Steric and Electronic Effects
for Transition Metal Catalysis
Yaşar GÖK, Seda KILIÇARSLAN, Halil Zeki GÖK, İlker Ümit KARAYİĞİT
Department of Chemistry, Faculty of Arts and Sciences, OsmaniyeKorkut Ata University, 80000
Osmaniye, Turkey.
Nowadays, the syntheses of enantiomerically pure compounds are of primary importance
due to containing stereogenic centers in a large amount of the pharmaceuticals and
agrochemicals. Catalytic enantioselective reactions are the most widespread way
because of obtaining a large amount of chiral target product with a small amount of
catalyst. Among the enantioselective catalysts, the use of transition metal complexes
containing chiral organic ligands is the most faced one [1].
Herein, we report the synthesis of optically pure ligands in a straightforward manner with
high yields and enantioselectivites (Figure 1). As part of our research on enantioselective
catalysis we decided to evaluate these chiral ligands in different enantioselective
reactions [2].
201
References:
[1] Jacobsen, E. N., Pfaltz, A., Yamamoto, H.,Springer, Berlin,1-3, 1999.
[2] (a) Gök, Y., Kekeç, L. Tetrahedron Lett. 55 (2014), 2727-2729. (b) Gök, Y., Küloğlu, S., Gök,
H. Z., Kekeç, L. Appl. Organometal. Chem. 28 (2014) 835-838.(c) Gök, Y., Gök, H. Z. Helv.
Chim. Acta98 (2015) 490-495.
202
Synthesis of Tungstophosphoric Acid Incorporated Mesoporous
Alumina Catalysts for Methanol Dehydration in DME Synthesis
M. İlker Şenera, Naime Aslı Sezgia,Timur Doğua, Gülşen Doğub, Nuray Oktarb
Chemical Engineering Department, Middle East Technical University, Ankara, 06800
b
Chemical Engineering Department, Gazi University, Ankara, 06570
a
Dimethyl ether (DME) is considered as a highly promising environmentally clean diesel
fuel alternate, which can be produced from synthesis gas. It has high cetane number
(55-60) and clean burning properties [1]. Possibility of using CO2 as the carbon source
in DME production makes this process even more attractive as a carbon neutral
technology. Production of DME from synthesis gas requires a bifunctional catalyst
combination, for methanol synthesis and dehydration functions. As for the methanol
synthesis function, commercial Cu-ZnO based catalysts are available. Heteropolyacids
with very high Bronsted acidity are considered as highly promising catalytic materials
for dehydration of methanol to DME [2, 3]. However, they have very low surface area
[3]. In the present study, tungstophosphoric acid incorporated mesoporous alumina
catalysts with high surface area and ordered pore structures were synthesized, to be
used as the methanol dehydration catalysts in DME synthesis. Mesoporous alumina
(MA) was synthesized by an evaporation-induced self-assembly (EISA) method [4],
using Pluronic-123 as the surfactant. In order to improve dehydration activity of this
material 5% TPA was impregnated on this material (MA), as well as on commercial
g-alumina (Toyo). Nitrogen physisorption results exhibit Type IV isotherms for both
MA (209.7m2/g) and commercial Toyo (147.7m2/g).Results revealed that impregnation
of TPA did not cause significant change of the structure of commercial g-alumina and
the synthesized materials had high acidity, which is required for methanol dehydration
in DME synthesis.
Acknowledgement
Financial support of TUBITAK through Project No. 115M377 is gratefully acknowledged.
References
[1] A. Ciftci, N. A. Sezgi, T. Dogu, Ind. Eng. Chem. Res. 49 (2010) 6753–6762.
[2] A. Thomas, C. Dablemont, J.M. Basset, F. Lafebre, C.R. Chimie 8 (2005) 1969–1974.
[3] D. Varisli, K. C. Tokay, A. Ciftci, T. Dogu, G. Dogu, Turk J Chem 33 (2009) 355– 366.
[4] A. Bayat, MSc Thesis, Middle East Technical University, Ankara, 2013.
203
Production of 2,6-Dimethylnaphthalene with Methylation of
Naphthalene over Au/Mordenite Zeolite Catalysts
Eda Karayılan1, Aysun Özen1, Fatih Güleç1, Ali Karaduman1
¹Ankara University Faculty of Engineering, Dept. of Chemical Eng. 06100 Ankara, TÜRKİYE
Methylation of Naphthalene is crucial reaction to obtain 2-Methylnaphtalene (2MN) and 2,6Dimethylnaphtalene (2,6-DMN). 2-MN is significant raw material for the
synthesis of vitamin K and 2,6-DMN [1,2]. 2,6 DMN is also one of the most important
Dimethylnaphtalene isomers in terms of used in precious polymers such as Polyethylene
naphthalate (PEN). PEN is valuable and expensive polymer which has better features
compare to Polyethylene terephthalate (PET) [2,3]. In this study, the effect of metal
doping and calcination temperature on the performance of Mordenite zeolite catalysts
were investigated for methylation of Naphthalene with methanol in order to enhance
2,6-Dimethynaphthalene (2,6-DMN) selectively. For catalyst preparation, 0.1 wt% Au was
doped on Mordenite catalysts using wet impregnation method and the catalystswere
calcined at two different temperatures (550°C and 750°C).The methylation experiments
were carried out in a fixed bed reactor at atmospheric pressure. The reactor was
operated at450°C, weight hourly space velocity (WHSV) was 2h-1, volume of catalystswas
2cm3(approximately 1g) and flow rate of inert carrier gas (N2) was selected10 ml/min.
Naphthalene, m-Xylene and Methanol mixture was prepared as a feedstock with mass
ratio of 1:3:5, respectively.The products were analyzed using a GC-MS which has 60
meter DB-1 capillary column. Conversion of Naphthalene, selectivity of 2-MN, 2,6DMN, DMNs, ratio of 2-MN/1-MN and 2,6-DMN/2,7-DMN were determined.
Acknowledgement
We are thankful and greatfully appreciate Ankara University Scientific Research Projects
(AÜ-BAP) for the support of this work. (Project No: 15B0443009)
References
[1] Park, J., Wang, J., Lee, C.W., Park, S., Bul.Korean Chem. Soc., 23, (2002),1011-1013.
[2] Zhao,L., Guo,X., Liu,M., Wang,X., Song, C., Chinese Journal of Chemical Engineering 18 ,(2010),
742-749.
[3] Niftaliyeva, A., Güleç,F., Şimşek,E,H., Güllü,M., Karaduman,A., Anadolu University Journal of
Science and Technology,16, (2015),167-178.
204
CHARACTERIZATION OF Ni/ZrTiO4CATALYSTFOR THE PARTIAL
OXIDATION of METHANE
Burcu Aygüna, Hasan Özdemira, M.A. Faruk Öksüzömera, Serkan Naci Koça
a
Processes such as coal gasification, dry reforming, steam reforming and partial oxidation
of hydrocarbons, are well known to be used for syngas production.Catalytic partial
oxidation of methane/natural gas (POM)into syngas has recently become a process
of the utmost interest due to its availability and low cost. The most active catalysts of
POM are based on Ni, Pt, Ru and Rh supported on irreducible metal oxides like Al2O3,
SiO2, ZrO2 etc. High catalytic performance and low price of Ni compared to noble
metals is an advantage, however Ni-based catalysts are prone to rapid deactivation due
to formation and sintering of active sites. Therefore, researches are concentrated on the
solvation of these problems.
The effect of the support on sintering and carbon deposition was investigated much
and pure supports, such as ceria and zirconia, have been shown to be especially efficient
for decreasing coke deposition by carbon gasification due to their oxygen storage
capacity [1]. TiO2 was also beneficial to decrease carbon deposition but deactivation
was prominent due to the formation of NiTiO3 [2].This formation could be prevented
maybe with the interaction of different metal oxides like ZrO2 to form ZrTiO4 structure.
In this work, ZrTiO4 support will be synthesized by using the sol-gel method and
characterized for POM which is not available in literature. For this purpose, 10(wt%) Ni
will beloaded onto ZrTiO4 and characterized by using BET, XRD and SEM analysis.The
reactions will be actualized with Microreactor-GC system, and it will be compared with
10(wt%) Ni/ZrO2 and Ni/TiO2 catalysis.
References
[1]W-S. Dong, K-W. Jun, H-S. Roh, Z-W. Liu, S-E. Park, Catalysis Letters, 78 (2002) 215-222.
[2] T. Wu, Q. Yan, H. Wan, Journal of Molecular Catalysis A: Chemical, 226 (2005) 41-48.
205
Characterization and Catalytic Performance of MnxOy-Na2WO4/
SiO2 for the Oxidative Coupling of Methane
Mahmut Yildiza,b*,Reinhard Schomaeckera
Department of Chemistry, Berlin Institute of Technology,10623 Berlin, Germany
b
Department of Chemistry, Gebze Technical University, 41400 Kocaeli, Turkey
a
Natural gas is still an underutilized resource for the production of valuable chemicals
and liquid fuels. On-site conversion of methane, the main constituent, to more useful
and value added chemicals (e.g. ethylene, methanol) could be of great importance for
using it more effectively in industry [1]. The oxidative coupling of methane (OCM)
to ethane and ethylene is one of the most important direct ways for methane
utilization. However, up to date, this reaction has not reached the stage of commercial
application, even though a large number of catalystshave been tested [2].Among the
known OCM catalysts, MnxOy-Na2WO4/SiO2 is a promising one in the literature for the
commercialization of an industrial process [3, 4].Despite the large number of studies on
this catalyst, structural characterizations are very difficult due to its complex supported
trimetallic and multiphase nature.
In the present study, the MnxOy-Na2WO4/SiO2 was characterized via ex-situ X-ray
diffraction, BET surface area, XPS surface composition, ICP chemical composition
analyses and TEM-SEM imaging techniques. Besides that in-situ X-ray diffraction
method was applied to detect which phases are present under reaction conditions and
during calcination process. Furthermore influences of reaction temperature, reactant
flow rate, catalyst bed dilution and calcination temperature of the catalyst on catalytic
performance were investigated. Moreover long-term catalytic activity experiments
(approx. 16 h) were performed in a packed-bed reactor made of quartz glass in order to
evaluate the stability of the catalyst.
References
[1] R. Horn, R. Schlögl, Catal.Lett. 145 (2015) 23-39.
[2] U. Zavyalova, M. Holena, R. Schlögl, M. Baerns, ChemCatChem 3 (2011) 1935-1947.
[3] X. Fang, S. Li, J. Lin, Y. Chu, J. Mol. Catal. (China) 6 (1992) 427-433.
[4] S. Arndt, T. Otremba, U. Simon, M. Yildiz, H. Schubert, R. Schomäcker, Appl. Catal. A-Gen.
425-426 (2012) 53-61.
206
The Effect of Metal Adding Sequence and Synthesis Media on
the Properties of SnSBA-15 Catalysts at Low Metal Ratio
Filiz AKTI a, Suna BALCI b, Timur DOĞU c
Hitit University, Chemical Engineering Department, 19030, Çorum
Gazi University, Chemical Engineering Department, 06570, Ankara
c
Middle East TechnicalUniversity, Chemical Engineering Department, 06531, Ankara
a
b
In this study, the effects of tinadding sequences to the synthesis solution and synthesis
media on the structural and chemical properties of tin loading SBA-15 catalysts
were investigated. The tin SBA-15 catalysts were obtained by using the tin metal
source as tin chloride and keeping the Sn/Si mole ratio as 0.03 in all synthesis. The
tin source was dissolved in the ethylalcoholor isopropyl alcohol and in the presence
of aluminumsulphate(Al/Si mole ratio: 0.001) and then added to the synthesis
solution before and after silica source (TEOS) addition. The synthesized catalysts
were characterized with nitrogen adsorption/desorption isotherms, XRD and FTIR
techniques. The BET surface area, total pore volumeand pore diameter valuesof SBA15 were increasedfrom 800 m2/g, 1.14 cm3/g and 6.73 nm to1027 m2/g, 1.49 cm3/g and
6.87 nmby metal loading,respectively. The surface area and total pore volume values
of catalysts prepared by dissolving the tin sourcein the isopropyl alcohol were higher
than that of the ethyl alcohol.While the tin addition after the TEOS caused decreases
in the surface area and total pore volume values, it wasn’t affectedthe pore diameter
values. The XRD results showed that thebasal spacing(d100), lattice parameter (a) and
pore wall thickness (δ) values of the SBA-15 were increased with the tin loading. The tin
adding sequence wasn’t caused much influence on these properties. The XRD patterns
showed thetinwas incorporated to the SBA-15 structure in the tin oxide form in all
catalysts. The FTIR analyses were performed after pyridine adsorption and it showed
that increase the peak intensitiesof acid sites and silanol groups in the structure with
metal loading. These peakintensities in the catalysts synthesizedby dissolving the tin
sourcein the isopropyl alcoholwere increased much more than the other catalysts.
207
Effect of Ti-Ce Contenton the Catalytic Activity of Alumina
Supported Catalysts in Selective Oxidation of H2S
H.Mehmet Tasdemirª, Yavuz Yagizatliª, Sena Yasyerliª, Nail Yasyerliª, Gulsen Doguª
ª Department of Chemical Engineering, Gazi University, 06570, Ankara
H2S is an important air pollutant and usually converted to elemental sulfur by using wellknown Claus process. The development of active catalyst is a necessity for the success
of Claus process. Iron, titanium and vanadium based catalysts showed high potential for
selective oxidation of H2S to elemental sulphur (H2S+1/2O2®S+H2O; 200°C≤T≤350°C)
[1–3]. In this study, alumina was synthesized by classical sol-gel method [4]. Alumina
(SG-Al2O3) supported Ti-Ce catalysts (Ti/Ce molar ratio of 4/1) with different weight
percentages (5%, 10% and 20%)were prepared by wet impregnation method. The
synthesized catalysts showed mesoporous structure. XRD patterns of sol-gel alumina
supported Ti-Ce catalysts showed the formation of maincharacteristic peaks of g-Al2O3
and amorphous structure. There was no peak corresponding to Ti and/or Ce in the XRD
pattern of the catalysts.Catalytic activities were tested in a fixed-bed flow reactor using
a feed stream containing stoichiometric ratio of H2S-O2 in He at 250°C. H2S conversions
and sulphur selectivities are given in Figure 1. Complete conversion of H2S was achieved
over Ti80Ce20@SG-Al2O3-10w and high sulphur selectivities (≥% 99) were obtained for
all catalysts. The EDS analysis of the used catalysts showed small amount of sulphur
deposition on the catalysts after reaction.
Figure1. H2S conversions and sulphur selectivities ( T=250°C, O2/H2S=0.5, Total flow rate= 100 mL/
min)
208
Acknowledgements
TUBITAK (114M185) is gratefully acknowledged.
References:
[1] D.D. Eslek Koyuncu, S. Yasyerli, Ind. Eng.Chem. Res., 48 (2009), 5223-5229.
[2] H.M.Tasdemir, S.Yasyerli, N. Yasyerli, Int. J. of Hydrogen Energy, 40 (2015), 9989-10001.
[3] V. Palma, D. Barba, Int. J. of Hydrogen Energy, 39 (2014), 21524-21530.
[4] E. Seker, N. Yasyerli, E. Gulari, C. Lambert, R.H. Hammerle, 208 (2002), J. of Catalysis,15–20.
209
INVESTIGATION and CHARACTERIZATION of Ni/MgO CATALYST
PREPARED BY ELECTROSPINNIG TECHNIQUE for the PARTIAL
OXIDATION and DRY REFORMING of METHANE
Burcu Aygüna, Hasan Özdemira, M.A. Faruk Öksüzömera, M. Ali Gürkaynaka
a
Methane, which is the main component of natural gas is generally used for residential
or industrial heating and generation of electrical power. Efficient use of natural gas have
raised interest in synthesis gas (CO+H2) production, which is necessary for methanol,
fuel and higher hydrocarbon synthesis. There are three well known methods for
the production of synthesis gas in literature and these methods are steam methane
reforming (SMR), carbon dioxide reforming of methane (CDR) and partial oxidation
of methane (POM). Researches about POM and CDR are still ongoing in the literature.
Figure 1: SEM photograph of 20(wt%)Ni/MgO catalyst prepared via electrospinning
technique, before (left side) and after calcination at 800°C for 5 h (right side)
Noble metals are relatively stable and active for the POM reaction but their high cost
and low availability limited their use in the reaction. Thus, nickel based catalysts are
considered to be good alternatives due to their high activity and selectivity. However,
carbon deposition and sintering are the main problems of these catalysts. Ruckenstein
et al. [1-2], was determined that the NiO/MgO catalyst had high activity and stability
due to formation of solid solution which limits the sintering and carbon deposition
to certain extent for POM and CDR reaction. Considering this fact, 20(wt%)Ni/MgO
catalyst (Figure 1) was prepared by a simple electrospinning technique and will be tested
for the POM and CDR reaction for the first time in literature. For the comparison, the
same catalyst will be synthesized with the wet impregnation method. The catalysts will
be characterized with BET, XRD and SEM analysis and the reactions will be actualized
with Microreactor-GC system.
210
References
[1]E. Ruckenstein, Y.H. Hu, Industrial & Engineering Chemistry Research, 37 (1998) 1744.
[2] H.Y. Wang, E. Ruckenstein, Appl. Catal.,204 (2000) 143–152.
211
THE CATALYTICACTIVITY OF AZO CONTAINING SCHIFF BASE
COMPLEXES
Mesut İKİZa, Esin İSPİRa
Department of Chemistry, Faculty of Science and Arts, Kahramanmaraş Sutçu Imam University,
Kahramanmaraş 46050-9, Turkey
a
Azo compounds with two phenyl rings separated by an azo (-N=N-) group, are
versatile molecules and have received much attention in research both fundamental
and application [1].A wide variety of cobalt(II) complexes are known to bind dioxygen
more or less reversibly and are therefore frequently studied as model compounds for
natural oxygen carriers and for their use in O2 storage, as well as in organic synthesis due
to their catalytic properties under mild conditions.
In the first systematic study on the catalytic activity of model copper complexes
towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) which contemplated both
mononuclear complexes and dinuclear complexes, Nishida et al. [2] found that in some
cases mononuclear complexes could be better catalysts that dinuclear ones.
Figure 1.
In continuance of the interest in syntheses of azo-based compounds, herein syntheses
and characterization of a series of azo-linked salicylidenic Schiff bases their metal
complexes, are reported. Also the oxidative C–C coupling properties of the CoII and CuII
complexes have been investigated on the sterically hindered 2,6-di-tert-butylphenol
(DTBP).
References:
[1].Nejati K, Rezvani Z, Massoumi B. Dyes Pigm., (2007);75:653.
[2]. L’Argentiere PC, Cagnola EA, Quitoga ME, Liprandi DA. Appl. Catal., A, (2002);226:253.
212
TRANSITION METAL COMPLEXES OF NOVEL CHROMONE SCHIFF
BASES: SYNTHESIS, CHARACTERIZATION AND CATECHOLASELIKE ACTIVITY
Cahit Demetgüla, Neslihan Beyazıta
a
Mustafa Kemal University, Faculty of Arts and Sciences, Department of Chemistry 31040Hatay
Catecholase enzymes, usually observed in plant tissues and in some insects and
crustaceans to catalyze the oxidation of catechols to the corresponding o-quinones are
type-3 copper active site proteins[1]. Consequently, the search for model complexes
capable of mimicking the function of catechol oxidases is primarily involved with
copper(II) complexes and complexes of other transition ions, particularly iron [2, 3]. In
this context, Fe(II) and Cu(II) Schiff-base complexes are interesting compounds because
of their capability to bind dioxygen reversibly and their catalytic activity in oxidation
reactions [4].
In this study, two new Schiff bases and their Cu(II) and Fe(II) complexes were synthesized
by condensation of two diamine compounds with 6-formyl-7-hydroxy-5-methoxy2-methylbenzopyran-4-one and by using appropriate metal salts, respectively (Figure
1). The prepared compounds were characterized by elementel analysis, FT-IR, and
NMR. In order to determine the kinetics parameters of catechol oxidase-like activity of
Schiff base metal complexes, the oxidation of the catechol derivative (3,5-DTBC) was
measured at 25°C by monitoring the increase of the absorption band at 390-400nm of
the product catequinone (3,5-DTBQ) derivative.
ec 2
n 1,5
a 1
b
r 0,5
so 0
b
A 300
3,5-DTBQ
H3 C
O
N
400
N
500
O
Wavelength (nm)
O
3,5-DTBC
O
M
O
O
O
[ML]
O
M= Cu(II) ve Fe(II)
Figure 1.Schiff base metal complex
Acknowledgments
This study has been supported by The Scientific and Technological Research Council of Turkey
(TÜBİTAK) through project no: 113Z604
213
References
[1] Panda, M.K.; Shaikin, M.M.; Butcher, R.J.; Gosh, P., Inorganica Chimca Acta 2011, 372(1),
145-151.
[2] Sarkar, S.; Sim, A.; Kim, S.; Lee, H., Journal of Molecular Catalysis A: Chemical 215, 410, 149159.
[3] Mal, S.K.; Mitra, M.; Biswas, B.; Kaur, G.; Bag, P.P. Reddy, C.M.; Choudhury, A.; Aliaga-Alcalde,
N.; Ghosh, R., Inorganica Chimica Acta 2015, 425, 61-66.
[4] Bnowmik, P.; Das, L.K.; Chattopadhyay, S.; Ghosh, A., InorganicaChimicaActa 2015, 430, 2429.
214
Hydrothermal Synthesis and Characterization of Heterogeneous
Catalysts for the Oxidation of the Thymol To Thymoquinone
Burak AY, Emel YILDIZ
Çukurova University, Department of Chemistry, Arts and Science Faculty, 01330, Adana
Some reactions of considerable commercial importance are: epoxidation of limonene
to limonene oxide; and oxidation of carvacrol or thymol to thymoquinone, a
compound with antitumor and hepatoprotective effects. In this vein, thymol can be
oxidized to thymoquinone (Fig. 1), which has a commercial value considerably higher
than that of the precursor. Since the natural sources of thymoquinone are limited to
certain plants such as Nigella sativa, Callitrisarticulate, there is a growing interest in its
production from other sources. It is well established that the chemical transformation
of abundant and cheap natural products can make available other more valuable
products [1].Thymol can be oxidized to thymoquinone only using metal catalysts.
Hydrothermal synthesis is an efficient method for the preparationof heterogeneous
catalysts because of advantages over other methods. [2]. In this study, we report the
hydrothermal synthesis and crystalstructure of Cu(II) and Ni(II) catalysts containing
pyridinedicarboxylic acid ligands. These catalysts were characterized by elemental
analysis, FT-IR, TGA, ICP and single crystal X-ray diffraction techniques. The metal
catalysts act asefficient heterogeneous catalysts and showed 100% selectivity on the
oxidation of thymol to thymoquinone.
Figure 1. Oxidation of thymol to thymoquinone using heterogeneous catalyst.
Acknowledgements
This work was financially supported by Çukurova University Research Fund (Project No: FBA-20165543).
References
[1] B. Ay, E. Yildiz, S. Jones, J. Zubieta, Inorg. Chim. Acta, 387 (2012) 15-19.
[2] J. Maa, X. Huang, R. Wei, L. Zhou, W. Liu, Inorg. Chim. Acta, 362 (2009) 3440.
215
SUITABLE CATALYST OBTAINING FOR ALKANE OXIDATION AND
ALKENE EPOXIDATION REACTIONS
Mehmet TÜMER, Muhammet KÖSE, Ferhan TÜMER
Chemistry Department, K.Maraş Sütcü Imam University, 46100, K.Maraş, Turkey
Finding the ideal catalyst [1] is one of the most intriguing challenges in chemistry today.
Interestingly, most often the strategy of empirical trial and error is applied still. This
trial-and-error-process can be accelerated e.g. with combinatorial or high-throughput
approaches or syntheses of multiple ligand derivatives. Additionally, one can study
the basic principles underlying catalysis, or improve the analytical tools. In this study,
we obtained the sterically hindered solid state polymer Schiff base ligands from the
reaction of the N- salicylidene (2,6-di-tert-butyl-4-imino)phenol with Merrifield resin
in the ethanol solution. The polymer anchored ligands were characterized by the
FTIR, SEM, TGA and DTA methods. Some transition metal complexes of the polymer
supported ligands were synthesized. The metal detection in the complexes was done
by ICP method. The oxidation and epoxidation properties of the metal complexes were
very high. SEM images of the Mn(II) complexes were given in Figure 1.
Figure 1. SEM images of the Mn(II) complexes.
References
[1] J.A. Gladysz, Pure Appl. Chem. 73 (2001) 1319
216
POLYMER SOLID SUPPORT CATALYSTS FOR ALKANE OXIDATION
Mehmet TÜMER, Muhammet KÖSE,Ferhan TÜMER
The oxidation of the organic compounds is one of the most important cycle reactions
in industrial chemistry. The immobilization of the homogeneous catalysts onto the solid
supports supplies potential for enlarging the utilities of the heterogeneous catalysts to
the homogeneous systems. In addition inorganic supports [1], the polymeric supports
have attained care because they are inert, nontoxic, nonvolatile, insoluble, and often
recyclable.In this study, we prepared three polymer-anchored Schiff base ligands and
their Cu(II), Co(II) and Ni(II) transition metal complexes (Figure 1). We did alkane
oxidation reactions of the metal complexes and used the cyclohexane and cyclooctane
as the substrate and they show the low activity. The metal complexes have not any
selectivity in the oxidation reactions. The polymer anchored Schiff base ligands and
their metal complexes have high thermal stability at higher temperatures.
Figure 1. PS-L2-M(II) for cyclohexane oxidation.
References
[1] B. K. Das, J. H. Clark, Chem. Commun., (2000) 605-606.
217
CATALYST DESIGN FOR ALKENE EPOXIDATION
Mehmet TÜMER, Muhammet KÖSE,Ferhan TÜMER
Transition metal complexes on polymer support have indicated various uses in
organic synthesis [1], curing agent for epoxy resin, as catalyst, as ion exchangeretc.
This technique of immobilization on an inert support have ground much care due
to their simple separation from the reaction mixture arrives to operational flexibility,
selectivity, efficiency, stability and ease of handling and economy in various industrial
processes.In this study, the Schiff base ligands were synthesized from the reaction of the
diamines 1,4-diamino butane, 1,4-diaminobenzene and trans-1,4-diaminocyclohexane
with 1,4-dihydroxy benzaldehyde in the ethanol solution. The imines prepared in this
way are formed in nearly quantitative yields and are of high purity.All compoundsare
very stable at room temperature in the solid state.In this study, we prepared three
polymer-anchored Schiff base ligands and their Cu(II), Co(II) and Ni(II) transition metal
complexes. Scanning electron micrographwas also recorded to investigate the surface
of the polymer-anchoring Schiff bases and their transition metal complexes. SEM
images of the free PS, PS-L3-Co, PS-L3-Ni and PS-L3-Cu complexes are shown in Figure
1.
Figure 1. SEM images of the Cu(II) and Ni(II) complexes.
References
[1] M. Roice, K. S. Kumar, V. N. R. Pillai, Tetrahedron, 56 (2000) 3725-3734.
218
New Ferrocene Based Schiff Bases Metal Complexes: Synthesis
and Investigation of Catalytic Activities
Gökhan CEYHANa
a
Technological and economic innovations often induce changes in the chemical
raw material used to produce goods organic chemicals [1].These reasons caused
olefins to replace acetylene in many commercial processes different decades ago.
Alkanes, however, are the least expensive and most abundant hydrocarbon resource
and thus represent an important potential feedstock for the chemical industry [2].
Unfortunately, very few selective methods are available for converting alkanes into
more significant products [3]. Furthermore, several desirable reactions utilizing alkanes
are not thermodynamically favorable at reasonable temperatures. New Ferrocene
based Schiff base metal complexes are used as a catalyst to initiate the radical oxidation
of cyclohexane using molecular oxygen from the air at 150 °C and 30 bar pressure. On
completion of the reaction, only 28% of CyH is converted to oxidized products and
with selectivity towards Cy=O and Cy-OH. In this paper were cyclo alkane oxidation
with new Ferrocene based Schiff base metal complexes investigated under microwave
irradiation. The Ru(III) and Pd(II) complexes showed good catalytic activity in the
oxidation of cyclohexane to desired oxidized products.
Figure 1. Catalytic oxidation of cyclohexane under microwave irradiation
219
References:
[1] G. Ceyhan, M. Köse, V. McKee, S. Uruş, A.l Gölcü, M. Tümer, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy, 382-398, (2012), 95.
[2] B. Retcher, J.S. Costa, J. Tang, R. Hage, P. Gamez, J. Reedijk, J. Mol. Catal. A:Chem. 286 (2008)
1–5.
[3] S. Tanase, J. Reedijk, R. Hage, G. Rothenberg, Top. Catal. 53 (2010) 1039–1044.
220
Oxidation of alkanes with hydrogen peroxide catalyzed by
ferrocene
Gökhan CEYHANa
a
Transition metal complexes, specially, iron derivatives, often play roles of good catalysts
in the oxidation of saturated and aromatic hydrocarbons with peroxides, especially with
green oxidants such as hydrogen peroxide [1,2]. In contrast, organometallic compounds,
particularly iron complexes, have so far been rarely used as catalysts in oxidation
processes [3].Ferrocene based Schiff base metal complexes are used as a catalyst to
initiate the radical oxidation of cyclohexane andcyclooctane using molecular oxygen
from the air at 185 °C and 60 bar pressure.In this paper were cyclo alkane oxidation with
Ferrocene based Schiff base metal complexes investigated under microwave irradiation.
The Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) complexes showed catalytic activity in the
oxidation of cyclohexane and cyclooctane to desired oxidized products.
Figure 1. Catalytic oxidation of cyclohexane under microwave irradiation
References:
[1] I. Gryca, B. Machura, J.G. Malecki, L.S. Shul’pina, A.J.L. Pombeiro, G.B. Shul’pin,Dalton Trans.
43 (2014) 5759-5776.
[2] M. Canta, D. Font, L. Gomez, X. Ribas, M. Costas, Adv. Synth. Catal. 356 (2014) 818-830.
[3]G.B. Shul’pin, in: A.J.L. Pombeiro (Ed.), Advances in Organometallic Chemistry and Catalysis,
Wiley, 2014, pp. 1-13.
221
Transition Metal Complexes of Ligand in a Liquid Crystal
Properties: Investigation of the Catalytic Activity
Gökhan Ceyhana*, Savaş Purtaşb
Research and Development Centre for University-Industry-Public Relations, K.Maraş Sütçü
İmam University, 46100, Kahramanmaraş Turkey
b
K.Maraş Sutcu Imam University, Faculty of Science and Letters, Department of Chemistry,
46100, K.Maraş.
a
The environmentally harmful oxidants are used in the endustrial oxidation processes
and there has been intensive investigation into developing oxidation processes which
utilize environmentally friendly oxidants such as molecular oxygen and hydrogen
peroxide [1]. However, suitable catalyst systems are required in order for these oxidants
to be implemented effectively on an industrial scale. In recent years there has been an
increase interest in transition metal complexes based on porphyrins, phthalocyanines
and Schiff bases [2]. The metal complexes of the polymer supported Schiff base
ligands are preferred in the heterogeneous catalytic systems. Inorganic and organic
polymers are used as a polymer support [3]. These are polymeric materials such as
the chloromethylated polystyrene(PS)-di(vinyl)benzene(DVB) [PS-DVB] resin, silanol,
poly(dichlorophosphazenes), zeolite, PVC. In this paper, we obtained a complex as
a single crystal and characterized by analytical and spectroscopic methods. Thermal
properties of the complexes were investigated by TGA and DSC methods. The
electrochemical properties of the complexes were studied in different solvents and at
various scan rates. The photoluminescence properties of the complexes in different
solvents and at different pH values have been investigated. Cyclo alkane oxidation with
Cu(II) complexes investigated under microwave irradiation.
Figure 1.The structure of the novel copper complexes.
References:
[1] C.J. Pereira, Chem. Eng. Sci. 54 (1999) 1959.
[2] M.T. Hassenein, S.S. Gerges, M.A. Abdo, S.H. El-Khalafy, J. Porphyr. Phthalocyan. 9 (2005)
621.
[3] D.C. Sherrington, Pure Appl. Chem. 60 (1988) 401.
222
Novel Gallic Esters: Its Synthesis, Structural Characterization,
Photoluminescence, Electrochemical Properties And Alkene
Epoxidation
Gökhan Ceyhana*, Savaş Purtaşb
Research and Development Centre for University-Industry-Public Relations, K.Maraş Sütçü
İmam University, 46100, Kahramanmaraş Turkey
b
K.Maraş Sutcu Imam University, Faculty of Science and Letters, Department of Chemistry,
46100, K.Maraş.
a
Epoxides are important classes of chemicals used extensively for the preparation of a
variety of fine or special chemicals such as natural products, drugs, polymer materials
[1]. Epoxides are highly useful intermediates for the production of a variety of important
commercial products and therefore their synthesis is a subject of substantial academic
and industrial interest [2]. Epoxides are well known as one of the most valuable building
blocks that can be used as intermediates and precursors for chemical production. The
oxidation of alkenes with aqueous hydrogen peroxide (H2O2) is very attractive from
the viewpoint of industrial production and synthetic organic chemistry, since aqueous
H2O2 is cheap, environmentally clean and easy to handle, and [3]. In this paper, we
obtained a novel gallic esters as a single crystal and characterized by analytical and
spectroscopic methods. Thermal properties of the gallic esters were investigated by
TGA, DTA and DSC methods. The electrochemical properties of the gallic ester were
studied in different solvents and at various scan rates. The luminescence properties of
the gallic esters in different solvents and at different pH values have been investigated.
Cyclo alkene epoxidation with gallic esters investigated under microwave irradiation.
Figure 1. Cyclohexane oxidation reaction.
References:
[1] YuLin Hu, J Iran Chem Soc (2015), 12, 2179–2184
[2] P. Farràs, Green Chem., (2016), 18, 255
[3] Weizheng Fan, Applıed Catalysıs A-General, (2015), 506, 173-179
223
Catalytic activity of Schiff Base Mn(III)/Co(III) complexes on
bleach catalyst
Büşra GENÇOĞLUa, Pınar Şena, Salih Zeki Yıldıza
a
Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYA,
TURKEY
The detergents of the next century will be routinely required to contain bleaching agents
that are not only more active than those currently available but also environmentally
safe and cost-effective. Hydrogen peroxide, are used as traditional bleaching agent [1].
However, it loses activity as the washing temperature decreases. In order to solved this
problem, bleach activator systems such as N,N,N’,N’-tetraacetylethylenediamine (TAED)
and nonanoyloxybenzene sulfonate (NOBS) have been developed and applied in many
laundry detergent [2]. Bleach activators are also effective at lower temperature (at 40oC
and above) due to having more oxidizing power than bare hydrogen peroxide [3].But
still lower temperatures are desirable. It is generally recognized that manganese and
iron complexes are less environmentally damaging reagents than other transition-metal
compounds, and such complexes have received considerable attention as bleaching
catalysts[4].
In this study we described new catalyst for oxygen-based bleaching as Schiff base
Mn(III)/Co(III) complexes. We evaluated the performance of the catalyst in bleaching
activity presence of hydrophilic and hydrophobic type of natural characteristic dyes.
References:
[1] R.G. Konsler, J. Karl, E.N. Jacobsen, J. Am. Chem. Soc. 120(1998) 10780
[2] G. Reinhardt, M.Loeffler, Tenside Surfact. Deterg. 1997, 34, 404.
[3] C. Xu, D. Hinks, A. El-Shafei, P. Hauser, M. Li, M. Ankeny, K. Lee, Journal of Fiber
Bioengineering&Informatics2011, 4, 209.
[4]M. Bösing , Bernt Krebs, B. Nestler, M. Seebach , G. Reinhardt, M. Wohlers, U. Dingerdissen,
Applied Catalysis A: General1999, 184, 273.
224
Catalytic Oxidation of Nitrogen Containing Compounds for
Nitrogen Determination
Alper SEVİNÇ1,2*, Gürkan KARAKAŞ1, İ. Bülent ATAMER2
Middle East Technical University , Chemical Engineering Department, Dumlupinar Blv., 06800
Ankara, Turkey
2
Research and Development Department, Terralab A.Ş., Dumlupinar Blv., 06800 Ankara, Turkey
1
High temperature catalytic oxidation of nitrogen containing compounds has great
importance for the analysis of environmental and industrial samples. The complete
oxidation of nitrogen in different functional groups, ammonia and nitrates to NO and
NO2 is a crucial step for the determination of nitrogen in samples[1,2]. In this study, the
catalytic activities of four different catalyst samples, CuO/ Al2O3, CuO-CeO2 / Al2O3
and Pt/ Al2O3, Fe2O3/ Al2O3 for total oxidation of nitrogen containing compounds
were analyzed. The catalyst samples were prepared to obtain a loading of 10% Cu,
3%Cu-7%Ce, 1% Pt, %5 Fe over the Al2O3 as a suppport by impregnation method.
Characterization of the catalyst samples was performed by X-ray powder diffraction
(XRD) and BET. EDTA, urea, ammonium nitrate, ammonium sulfate, pyridine, glutamic
acid were selected as model components representing various nitrogen functional
groups. The experiments were performed in a quartz tubular reactor in two zone furnace
and the sample first oxidized at 700-850 oC under air flow of 500 ml/min and the waste
gases treated in second zone at 700oC over catalyst bed. The catalytic activities of the
samples were investigated by mass spectrometry by analyzing combustion products.
According to experiments results, Fe2O3/ Al2O3 and Pt/ Al2O3 catalysts showed good
catalytic activity for all nitrogen containing model compounds ;however, CuO/ Al2O3,
CuO-CeO2 / Al2O3 were found to be poorcatalytst for the oxidation of nitrogen of
pyridine and ammonium nitrate.
References:
[1]: Merriam, J., Mcdowell, W., & Currie, W. (n.d.). A High-Temperature Catalytic Oxidation
Technique for Determining Total Dissolved Nitrogen. Soil Science Society of America Journal,
1050-1050.
[2]: Chen, C., Xu, Z., Keay, P., & Zhang, S. (n.d.). Total soluble nitrogen in forest soils as determined
by persulfate oxidation and by high temperature catalytic oxidation. Australian Journal of Soil
Research, 515-515.
225
Catalytic Properties of ONO Type Salicylaldimine Copper(II)
Complexes
Gökhan Ceyhana,b, Münire Sarıgüla, Muhammet Kösea, and Mukerrem Kurtoglua
Department of Chemistry, Kahramanmaraş Sutcu Imam University, 46100, Kahramanmaraş
Turkey
b
a
Azo compounds are versatile molecules that find widespread applications as dyes and
pigments in textile industry. They also have advanced applications in organic synthesis
and high technology areas such as laser, liquid crystalline displays and ink-jet printers
[1].Three azo-Schiff base copper(II) complexes were used as a catalyst to initiate the
radical oxidation of cyclohexane using molecular oxygen from the air at 180 °C and 45
bar pressure.. In this paper were cyclo alkane oxidation with azo-Schiff base copper(II)
complexes investigated under microwave irradiation. Catalytic activities of the copper
complexes were investigated at different conditions and the results were compared
with the literature data. These complexes were found to be active in the catalytic
oxidation of some hydrocarbons, such as cyclohexane and cyclooctane.
Figure: The proposed structure of the new Cu(II) complexes used as catalysts.
References
[1] M.Sarigul, P. Deveci , M. Kose, U. Arslan, H. Türk Dagi, M. Kurtoglu. J. Mol. Struct. 1096
(2015) 64–73
226
Copper Complexes with Bidentate NO Ligands as Novel Catalysts
for the Homogeneous Partial Oxidation of Alkanes
Gökhan Ceyhana,b, Sevgi Kahramana, Muhammet Kösea, and Mukerrem Kurtoglua
Department of Chemistry, Kahramanmaraş Sutcu Imam University, 46100, Kahramanmaraş
Turkey
b
Research and Development Centre for University-Industry-Public Relations, Kahramanmaras
a
Azo-azomethines are known to be interesting because of theexistence of both
hard nitrogen and/or oxygen donor atoms inthe backbones of these compounds,
some of which have interestingphysical and chemical properties [1].The transition
metalcomplexes have been widely used as a powerful tool in catalytic reactions which
has an active role in developingchemical science and technology by the design new
types of funtional ligands and useful new synthetic methods.Selective oxidation of
hydrocarbons is an important phenomena in view of the economical and ecological
use of naturalraw materials. However, catalytic oxidation of unactivated hydrocarbons
remains as a challengingtopic due to the high activation energy of the C-H bond. In this
work, two new azo-azomethine ligands, which were synthesised previously in our group
[2], based copper complexes were synthesised and used as catalysts in the oxidation
process of cyclohexaneand cyclooctane under microwave irradiation.
Figure: The proposed structure of the new Cu(II) complexes.
References
[1] H. Khanmohammadi, M. Erfantalab, A. Bayat, A. Babaei, M. Sohrabi, Spectrochim. Acta A 97
(2012) 876.
[2] S. Eskikanbur, K. Sayin, M. Kose, H. Zengin, V. McKee, M. Kurtoglu. J. Mol. Struct. 1094
(2015) 183–194
227
The comparison of catalytic activity of non-ionic and ionic
Mn(III)/Co(II) Phthalocyanine complexes on bleach systems
Pınar ŞENª, Salih Zeki YILDIZª
a
Sakarya University, Faculty of Arts and Sciences, Department of Chemistry, 54187, SAKARYA,
TURKEY
Oxidation reactions are of great importance in the chemical industry. Hydrogen
peroxide and molecular oxygen are used as potent oxidant frequently [1]. But, their
activity is kinetically low under many experimental conditions. In further studies such
as design and development transition metal complexes have attracted great attention
due to catalyze substrate oxidation effectively by hydrogen peroxide or molecular
oxygen [2]. In addition to using in organic synthesis, hydrogen peroxide based on bleach
catalyst play a major role for the pulp and paper production, waste water treatment
and laundry for industrial or domestic applications [3].
So far, several novel coordination compounds of salen, saltren, terpyridine-type ligands
and triazole derivatives,possessing significant potential in activating hydrogen peroxide,
have been synthesized and tested in bleach process[4]. Several transition metal
complexes were reported for the mentioned compounds. Specifically, manganese
and iron complexes are preferred as promising bleach catalyst due to environmental
compatibility and toxicological point of view[5].
In this study we described new catalysts for oxygen-based bleaching as Mn(III) and
Co(II) phthalocyanine compounds. We evaluated the catalytic performances of the
prepared catalysts in bleaching process presence of hydrophilic and hydrophobic type
of natural characteristic dyes and H2O2.
References:
[1] G. Parshall, S.Ittel, Homogeneous Catalysis1994, Wiley
[2] J.C. Terrence Acc. Chem. Res. 27 (1994) 279-285
[3] J.I. Kroschwitz, M. Howe-Grant Kirk-Othmer, Encyclopedia of Chemical Technology, 4rd ed.
Wiley: New York, 1991
[4] T. Wieprecht, J. Xia, U. Heinz, J. Dannacher, G. Schlingloff, Journal of Molecular Catalysis A:
Chemical, 203 (2003) 113–128.
[5] M. BoÈsinga , B. Krebsa, B. Nestlerb, M. Seebachb , G. Reinhardtb , M. Wohlersc , U.
Dingerdissenc Applied Catalysis A: General, 184 (1994) 273-278.
228
THE CATALYTIC ACTIVITY OF NOVEL, AZO-CONTAINING SCHIFF
BASES AND THEIR METAL COMPLEXES
Ayşe İNANa, Mesut İKİZa, Esin İSPİRa
a
Department of Chemistry, Faculty of Science and Arts, Kahramanmaraş Sutçu Imam University,
Kahramanmaraş, 46050-9, Turkey
Among the various ligand systems, Schiff base analogues have attracted great interest
in recent years. Azo group show donor properties and play an important role in
coordination chemistry [1]. A wide variety of cobalt(II) complexes are known to
bind dioxygen more or less reversibly and are therefore frequently studied as model
compounds for natural oxygen carriers and for their use in O2 storage, as well as in
organic synthesis due to their catalytic properties under mild conditions. [2].
Because of the importance of azo-containing Schiff base compounds and in
continuance of the interest in syntheses of azo-based compounds, herein syntheses
and characterization of a series of azo-linked salicylidenic Schiff bases and their CoII and
CuII complexes were reported and their structures were confirmed elemental analysis,
IR and UV-visible spectral data.
Figure 1.
The analytical data shows that the metal to ligand ratio in the mononuclear Schiff
Base complexes is 1:2. Also the oxidative C–C coupling properties of the CoII and CuII
complexes have been investigated on the sterically hindered 2,6-di-tert-butylphenol
(DTBP).
References:
[1]. Z. Shaghaghi, Spectrochim Acta A, 131 (2014) 67-71.
[2]. Tümer M, Ekinci D, Tümer F, Bulut A, Spectrochim. Acta, Part A, (2007); 67:916.
229
Investigation of Oxidation Reaction Pathways of Oxygenates on
Au(111) Single CrystalDepending on the Behaviour of Oxygen
Mustafa Karatoka, Evgeny Vovkb,Asad A. Shaha, Emrah Ozensoya,*
Boreskov Institute of Catalysis,830090, Novosibirsk, Russian Federation
a
b
Recently, it has been demonstrated that gold is very active and selective in various
partial oxidation (PO) processes and oxidative coupling (OC) reactions [1,2]. However,
the behaviour of oxygen species on Au(111) is still under debate [3]. In the current work,
we investigated the behavior of adsorbed atomic oxygen layers on the Au(111) model
catalyst surface and their reaction with probe molecules, such as CO and methanol.In
addition, oxidation reaction of acetaldehyde was investigated under the most active
conditions on the Au(111) surface; formation of PO and OC reaction products were
demonstrated. Atomic oxygen was created on Au(111) and noticed that it’s reactivity
towards CO changes depending on the temperature of the catalyst.TPD desorption
profiles of adsorbed oxygen on Au(111) at different temperatures before and after CO
exposure are shown in Figures 1 a and b. Figure 1c shows O1s XP spectra demonstrating
the presence of three different oxygen species as a function of surface oxygen coverage.
The most active surface corresponded to a low-coverage of oxygen exposed to the
surface at 140 K temperature. Under these conditions, oxidation of acetaldehyde yields
acetic acid and methyl acetate as a PO and OC products; respectively (Figure 1d).
Figure 1. TPD patterns of O/Au(111) prepared at (a) 460K, (b) 140K; (c) O1s XP spectrum of oxygencovered Au(111); (d) TPRS patterns of acetaldehyde oxidation reaction on O/ Au(111)under the most
reactive conditions.
References
[1] B. Xu, R.J. Madix, C.M. Friend, Acc. Chem. Res., 47 (2014) 761-772.
[2] X. Liu, L. He, Y. Liu, Y. Cao, Acc. Chem. Res. 47 (2014) 793-804.
[3] J. Gong, C.B. Mullins, Acc. Chem. Res., 42 (2009) 1063-1073.
230
Effective Catalysts Derived from Carbazole for Alkene oxidation
Selma Bal
Kahramanmaras Sutcu Imam University, Faculty of Sciences and Literature, Department of
Chemistry, 46100, Kahramanmaras, Turkey.
Among alkene epoxidation reactions, styrene and cyclohexene oxidation reactions
captured quite high attention due to their versatile usage as strating materials in
many synthetic organic reactions. Schiff base ligands and their metal complexes have
been exensively used in many oxidation reactions of different organic compounds
as catalysts[1,2]. With this work, Carbazole derived two novel ligands and their Cobalt
(II), Manganese (II) and Nickel (II) coordination compounds have been synthesized
and characterized through various spectroscopic techniques (Figure 1). Synthesized
compounds have been examined for their catalytic activities in the oxidation reactions
of styrene and cyclohexene.
Figure 1. Synthesized coordination compounds from Carbazole
References
[1] Maiti M, Sadhukhan D, Thakurta S, Zangrando E, Pilet G, Signorella S, Bellú S, Mitra S, B
Chem Soc Jpn, 87 (2014):724-732.
[2] Mavrogiorgoua A, Papastergioua M, Deligiannakis Y, Louloudi M, J Mol Catal A-Chem
393(2014):8-17.
231
Schiff base transition metal complexes with ceftazidime:
Synthesis and Investigation of Alkane Oxidation
Ozge Erena, Harun Muslub, Gökhan Ceyhanc, Mehmet Tumera and Aysegul Golcua*
Department of Chemistry, Faculty of Science and Letters, Kahramanmaras Sutcu Imam
University, 46100, Kahramanmaras, Turkey.
b
Afsin Vocational High School, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras,
Turkey.
c
K.Maraş Sutcu Imam University, ÜSKİM, 46100, K.Maraş
a
Ceftazidime (INN) is a third-generation cephalosporin antibiotic. Cephalosporins are the
second major group of h-lactam antibiotics, they are classified into four generations. The
biological activity of these antibiotics is the h-lactam ring [1]. The possible interaction
that may occur between metal ions and these antibiotics is of importance as this
may affect the drug absorption through the human membrane. Cyclohexane (Cy-H)
oxidation into cyclohexanol (Cy-OH) and cyclohexanone (Cy=O) has a importance
in industry. Over a billion tones of Cy=O and Cy-OH are produced each year and are
generally used for the synthesis of Nylon-6 and Nylon-6,6 [2]. Schiff base transition
metal complexes with ceftazidime are used as a catalyst to initiate the radical oxidation
of cyclohexane using molecular oxygen from the air at 160 °C and 15 bar pressure.
On completion of the reaction, only 19% of CyH is converted to oxidized products
and with selectivity towards Cy=O and Cy-OH. Tanase has synthesized polydentate
pyridine based ligand and its iron complexes [3]. These complexes were active in the
catalytic oxidation of some hydrocarbons, such as cyclohexane and cyclooctane[3].
In this paper werecyclo alkane oxidation with Schiff base transition metal complexes
with ceftazidime investigated under microwave irradiation. The Ru(II),Fe(III) and Ni(II)
complexes investigate catalytic activity in the oxidation of cyclohexane to desired
oxidized products.
References :
[1] Williams DR (1971) The metals of life. Van Nostrand Reinhold, London
[2] B. Retcher, J.S. Costa, J. Tang, R. Hage, P. Gamez, J. Reedijk, J. Mol. Catal. A:Chem. 286 (2008)
1–5.
[3] S. Tanase, J. Reedijk, R. Hage, G. Rothenberg, Top. Catal. 53 (2010) 1039–1044.
232
Drug metal complexes: Synthesis and Investigation of Alkane
Oxidation
Ozge Erena, Derya Kılıcaslanb , Gökhan Ceyhanc, Mehmet Tumera and Aysegul Golcua*
Department of Chemistry, Faculty of Science and Letters, Kahramanmaras Sutcu Imam
University, 46100, Kahramanmaras, Turkey.
b
Afsin Vocational High School, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras,
Turkey.
c
K.Maraş Sutcu Imam University, ÜSKİM, 46100, K.Maraş
a
Cefotaxime (INN) is a third-generation cephalosporin antibiotic. Cephalosporins are the
second major group of -lactam class of antibodies with broad spectrum of antimicrobial
properties. Their antibacterial and pharmacokinetic properties have wide therapeutic
use.[1]The cefotaxime drug was used for complexs formation reaction with Cd(II),
Pd(II), Ru(II) and Zn(II) metal salts have been synthesized. Then, these complexes have
been characterized by spectroscopic and analytical techniques. Thermal behavior of
the complexes were also investigated. The electrochemical property of complexes have
been investigated by cyclic voltammetry (CV).In this paper werecyclo alkane oxidation
with Drug transition metal complexes with cefotaxime investigated under microwave
irradiation. The Cd(II), Pd(II), Ru(II) and Zn(II) complexes investigate catalytic activity
in the oxidation of cyclohexane to desired oxidized products.
References:
[1] Williams DR (1971) The metals of life. Van Nostrand Reinhold, London
233
Synthesis and Characterization of MCM-41 Supported Ni
Catalysts for Acetic Acid Steam Reforming
N. Çakıryılmaz1, H. Arbağ1, N. Oktar1, G. Doğu1, T. Doğu2
GaziUniversity, Department of Chemical Engineering, 06570 Ankara, Turkey;
Middle East Technical University, Department of Chemical Engineering, Ankara, Turkey.
1
2
Developments in fuel cell technology opened new horizons for the production
of hydrogen, which is considered as a promising clean energy carrier. Production of
hydrogen from non-fossil renewable resources has been considered to have significant
environmental and economical advantages. Hydrogen can be produced by steam
reforming of acetic acid, which isobtained as the by-product of biomass pyrolysis. Recent
research in this area is focused on the development of active and stable catalysts, to
increase hydrogen yield and decrease coke and CH4 formation [1-3]. In this study, nickel
incorporated mesoporous MCM-41 catalysts withhigh surface area were synthesized
for the reforming reaction of acetic acid. The catalysts were reduced at 750oCprior
to the activity tests. Catalysts were characterized by XRD, N2 adsorption-desorption,
DRIFTS and SEM techniques. N2 Adsorption-Desorption isotherms of pure and nickel
incorporated MCM-41 catalysts were consistentwith Type IV isotherms and surface
area of bare MCM-41 was found as 1213m2/g. XRD analysis of thesematerials showed
characteristic peaks corresponding to MCM-41 and metallic Ni. Activity test of Ni
impregnated material (10 %wt) (10Ni@MCM-41), which was performed at 750oC(with
a feed stream containing AceticAcid/H2O/Ar =1/2.5/2) gave highly promising results
to achieve high hydrogen yields.Results indicated high and stable activity in steam
reforming of acetic acid with an acetic acid conversion of 100%. Coke formation was
not also high over the spent catalysts.
Acknowledgement
Reference
[1] Basagiannis A. C.,Verykios X.E., ‘Catalyticsteamreforming of aceticacidforhydrogenproduction’,
International Journal of HydrogenEnergy, 32(2007), 3343–3355.
[2] Iwasa, N.,Yamane, T., Takei, M., Ozaki, J., Arai, M., “Hydrogenproductionbysteamreforming
of aceticacid: Comparison of conventionalsupported metal catalystsand metalincorporatedmesoporoussmectite-likecatalysts”, International Journal of HydrogenEnergy, 35
(2010), 110-117
[3]Pant, K.K.,Mohanty, P., Agarwal, S., Dalai, A.K., “Steamreforming of aceticacidforhydrogenprodu
ctionoverbifunctionalNi-Cocatalysts”, CatalysisToday, 207 (2013), 36-43.
234
COMPARISON OF FRESH FCC CATALYSTS, E-CAT SAMPLES and
FCC ADDITIVES FOR COMPREHENSION OF THE PROCESS
Deniz Onay Atmacaa, Melek Bardakcı Türkmena, Burcu Yüzüaka, Ayşegül Bayata,
Ersen Ertaşa
Turkish Petroleum Refineries Co., R&D Department, Körfez, Kocaeli, 41790
a
Catalytic cracking processes are used for producing lighter products such as LPG,
gasoline, naphtha, kerosene and diesel fuels from the crude oil. Aerated catalyst flows
like a liquid in fluid catalytic cracking (FCC) process for the production of gasoline
from high boiling point fractions [1]. Circulating catalyst samples, named as e-cat, are
taken from FCC unit. Analysis of e-cat samples reveals valuable information related with
the on-going performance conditions of the process. Additives are introduced into the
FCC units for both performance improvement of the unit and environmental aspects
in terms of reduction of emissions such as SOx, NOx and CO.Particle size distribution
(PSD), surface area, sodium and rare earth content in weight % are several important
characterization properties of the fresh FCC catalysts. PSD indicates the fluidization
properties of the catalyst and surface area is highly related with the activity of the
catalyst. Since deactivation of the zeolite is observed due to the presence of sodium,
sodium content should also be monitored. Catalytic activity and hydrothermal stability
of the catalyst is attained by the rare earth content [2]. In addition to the comparison
between different type of FCC catalysts and additives; fresh FCC catalysts, e-cat samples
and e-cat samples after introduction of an additive areinvestigated in terms of XRD,
XRF, BET, PSD and TGA analysis to understand the difference of the phases throughout
the process of the FCC unit.
References
[1] David S.J. Jones, Peter R. Pujado, Handbook of Petroleum Processing, Springer, 2006
[1 ]Reza Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Professional Publishing, 2nd
Edition, 2000
235
Hydrogen Adsorption on M2+-LTL Zeolite Clusters (M = Be, Mg
and Ca) : A Density Functional Theory Study
Mehmet Ferdi FELLAHa
a
Bursa Technical University, Chemical Engineering Department, Bursa, TURKEY
Since the fossil hydrocarbon resources have been becoming limited, the concept of
using hydrogen as a future energy vector has been important for the last three decades.
Large scale and safe hydrogen storage should be developed [1]. There are several
hydrogen storage methods such as pressurized, cryogenically cooled, vessels containing
an adequate adsorbing material. Among adsorbents for hydrogen adsorption, active
carbon, zeolites, and several metal alloys are most significant candidates [2]. The aim
of this study is to investigate the activity of [M]2+ sites in LTL (Linde Type L) zeolite
(where M = Be, Mg and Ca) for the hydrogen adsorption. All calculations in this study
were based on Density Functional Theory (DFT) [3] as implemented in the Gaussian
09 software [4]. The hydrogen adsorption capacities of M2+-LTL clusters have been
analyzed by using B3LYPmethod [5,6] with 6-31G(d,p) basis set. Since DFT calculations
on cluster or periodic zeolite models generally predict very similar reactivity trends [7].
The 24T LTL cluster was used. Two Al atoms were placed in T8 cycle of the framework.
The 24T LTL cluster was modeled as [Si22Al2O64H32]2-. [M]2+ sites where M = Be, Mg and
Ca have been used to obtain a neutral cluster. Metal atoms are only located on oxygen
atoms of the T8 structure. The dangling bonds of the terminal silicon atoms were
terminated with H atoms. All atoms of the cluster (except terminating H atoms) and
the adsorbing molecules were kept relaxed. The optimized geometries for the clusters
were obtained with neutral charge and singlet spin multiplicity. In order to determine
the hydrogen adsorption energy on metal exchanged LTL clusters, H2 molecule was
adsorbed on metal site of LTL clusters by Equilibrium Geometry (EG) calculations. H2
adsorption energy values were computed as -3.1, -28.8 and -11.8 kJ/mol for Be-, Mg- and
Ca-LTL clusters.
(This work has been supported by Research Fund of the Bursa Technical University.
Project Number: 2015-01-005)
References
[1] A.A. Strub, G. Imarisio, Hydrogen as an Energy Vector, D. Reidel, Dordrecht, (1980)
[2] http://www1.eere.energy.gov/hydrogenandfuelcells/storage
[3] W. Kohn, L. Sham, J. Phys. Rev. 140 (1965) A1133-A1138.
[4] M. J. Frisch et al. Gaussian 09; Gaussian, Inc.: Wallingford, CT, (2009).
[5] A. D. Becke, Phys. Rev. B 38 (1988) 3098-3100.
[6] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37 (1988) 785-789.
[7] M. F. Fellah, J. Phys. Chem. C 115 (2011) 1940-1951.
236
Investigation of Surface Acidity of Metal/Bimetal Modified
Zeolite Catalysts using Pyridine Probe Molecule by FT-IR
Hülya MADENCİOĞLU and Ali KARADUMAN
Ankara University Faculty of Engineering, Dept. of Chemical Engineering 06100 Tandoğan,
Ankara - TURKEY
Nowadays using of synthetic zeolites increases due to their properties as high surface
area, large pore sizes, high adsorption capacities and replaceable active sites. Otherwise,
zeolites contain aluminum, silicium and oxygen in the three-dimensional structure of
different properties can be prepared by making changes such as dealumination[1].
Catalytic activities of zeolites are associated with acid sites where in surfaces directly.
Therefore, in the zeolite for use as catalyst, acidity is significant[2]. In literature researches,
there are two types as Lewis and Bronsted acidity[3]. In the characterization process of
the acid sites, a wide number of techniques are used, such as: titration, temperature
programmed desorption and the adsorption of basic probe molecules. In the present
work, pyridine as a probe molecule was added over the catalyst and the location and
amount of pyridine which connected to acid sites is determinated by FT-IR[4].
In this paper, modified zeolites were prepared with MCM-41, Y, Beta and ZSM-5 zeolites
with metal (Cu, Ni, Co, La, Zr, Pd, Rb) and bimetal(Cu-Zr, Ni-Co) by impregnation
method. Metal/ bimetal modified zeolites were mixed at a certain rate with KBr and
FT-IR spectra was taken. When pyridine was used, Bronsted acidity of characteristic
peaks was around 1540- 1640 cm-1 and Lewis acidity of characteristic peaks was around
1450- 1620 cm-1. Obtained results was evaluated with these information. There was no
significant difference observed between pure and metal/ bimetal modified MCM-41,
Y, Beta and ZSM-5 zeolite catalyst. According to acidity tests, the highest Lewis acidity
peak is observed with pure MCM-41. MCM-41 and Y zeolite catalyst impregnated with
metal were observed to reduce peak intensities. There was found different result from
others for Beta zeolites catalyst, acid peaks was reached highest value in Ni-Co/ Beta
catalyst. In ZSM-5 zeolite catalysts, characteristic peaks was increased with pyridine
which was added the structure.
References:
[1] Sadowska, K., Gora-Marek, K., Datka, J., Vibrational Spectroscopy 63 (2012) 418- 425.
[2] Jin, F., Li, Y., Catalysis Today 145 (2009) 101-107.
[3] Silva, M., Silva, F., Claudio, A., Tellez, S., SpectrochimicaActa Part A 58 (2002) 3159- 3166.
[4] Meloni,D., Laforge, S., Martin, D., Guisnet, M., Rombi, E., Solinas, V., Applied Catalyst A:
General 215 (2001) 55-66.
237
Synthesis and Characterization of CMK-3 and Activated Carbon
Based Catalysts
Gülce ÇAKMANa , Nahide NARİNa, Feza GEYİKÇİa
OndokuzMayis University, Faculty of Engineering, Department of Chemical Engineering, 55139, Samsun
a
Carbons can be used in many areas. One of such areas is H2/O2 PEM fuel cells in which
they can be used as a catalyst support. The carbon based catalysts can be used anode
and cathode reactions in H2/O2 PEM fuel cells. Because ofoxygen reduction reaction
isslow, the catalysts will be used at cathode side to accelerate.The purpose of this study
is to improve the catalyst properties in which used in our previous study [1]. Some of
important properties of carbonare having high BET surface area, pore dispersion, pore.
In this study, CMK-3 and activated carbon will be produced. CMK-3 carbon synthesis
route is first started by silica (SBA-15) production. For this purpose, SBA-15 will be
synthesized and will be used as template for carbon production. The second catalyst
support will be produced from biomass via pyrolysis. Since biomass is cheap and ecofriendly, it was preferred.Rapid and simple synthesis route of biomass based activated
carbon is widely use for various catalytic applications.
After carbon productions, metal or bimetallic (such as Ni, Pd, Pt, etc.) will be covered
to carbons by using microwave method for different power. The effect of power is
investigated for metal distribution on carbon surface. Structural characterizations of
the carbon support and catalyst will be analyzedby using SEM, N2 adsorption, XRD and
TGA analysis. Synthesis and characterization results of these materials will be presented.
References
[1] Fıçıcılar, B., Çakman, G., Narin, N., Geyikçi, F., 2015, CMK-3 carbon based
electrocatalysts for use in regenerative fuel cells, Porous and Powder Materials
Symposium and Exibition, İzmir, Türkiye, 15-18 Eylül.
238
IMPACT OF HYDROCRACKING CATALYST CHARACTERISTICS ON
THE PERFORMANCE OF HYDROCRACKING UNIT
Melek Bardakcı Türkmena, Burcu Yüzüaka, Ayşegül Bayata, Deniz Onay Atmacaa,
Ersen Ertaşa
Turkish Petroleum Refineries Co., R&D Department, Körfez, Kocaeli, 41790
a
Hydrocracking is a refining technology which is used for the conversion of a variety
of feedstocks to a range of products by adding hydrogen, removing impurities in the
presence of catalyst. Hydrocracking feeds, with higher molecular weights and lower
hydrogen/carbon ratios can range from heavy vacuum gas oils and coker gas oils to
atmospheric oils where products, having a lower molecular weight with higher hydrogen
content and a lower yield of coke, usually range from heavy diesel to light naphtha
[1, 2]. Catalysts for heavy oil hydrocracking require optimum catalyst characteristics
to process heavy molecules that presents in VGO type feedstock in order to obtain
high middle distillate yield and conversion. This study covers the investigation of the
impact of hydrocracking catalysts characteristics on the performance of commercial
hydrocracking unit. Five different unit performance data have been gathered which
belong to four different catalyst systems. Unit performance data include operation
parameters, middle distillate selectivity, conversion, feed properties and diesel features.
The catalysts were characterized by number of techniques and measurements, such
as BET surface area, pore volume, pore size, XRD, XRF, TPD acidity and TGA thermal
stability. It has been found that the catalyst system withhigh porosity,strong acidic
function and low silica/alumina ratio delivers outstanding feed conversion and middle
distillate selectivity performance.
References
(1)Speight J. G. and Özüm B., Petroleum Refining Process, Marcel Dekker Inc., 2002, pp. 485-499
(2)David, S.J. Jones and Peter R. Pujado, Handbook of Petroleum Processing, Springer, 2006, pp
287-300, 308-306
239
AMMONIA DECOMPOSITION REACTION OVER ZEOLITE Y
SUPPORTED IRON CATALYSTS: EFFECT OF DEALUMINATION
Yeliz DURAK-ÇETİNa,c, Şerife SARIOĞLANb, Alper SARIOĞLANa,Hasancan OKUTANc
TÜBİTAK Marmara Araştırma Merkezi, Enerji Enstitüsü, P.K.21, 41470 Gebze, Kocaeli
TÜBİTAK Marmara Araştırma Merkezi, Kimyasal Teknoloji Enstitüsü, P.K.21, 41470 Gebze,
Kocaeli
c
Kimya Metalurji Fakültesi, Kimya Mühendisliği Bölümü, İstanbul Teknik Üniversitesi, 34469
Maslak, Istanbul
a
b
Gasification, is a thermochemical conversion technology applied for the production of
synthetic fuels and chemicals from coal and biomass. A syngas containing H2 and CO is
released as a result of gasification reaction. Synthetic fuels and chemicals are produced
from syngas through the Fischer-Tropsch (F-T) method. Nitrogenous (NH3, HCN) and
sulfurous (H2S, COS) pollutants are formed in ppm level depending upon the content of
the gasified solid fuel and lead to the poisoning of the F-T catalysts. Therefore, it is a must
to reduce the levels of these pollutants below 1 ppmv in syngas [1]. NH3 concentrations
can be reached up to 4000 ppmv in syngas as a function of the nitrogen content of the
solid fuel [2]. NH3 removal can be achieved via three different ways, namely scrubbing,
selective oxidation and catalytic decomposition [3]. NH3 decomposition reaction is a
most promising way of NH3 abatement since it gives the H2 generation opportunity. In
this study, zeolite supported catalysts has been prepared to have an iron (Fe) content
of 10% via wet impregnation method, characterized and tested. HY zeolites with two
different SiO2 to Al2O3 ratios of 5.2 and 80 and dealuminated forms of HY (5.2) zeolite at
two different hydrothermal dealumination temperature (350°C and 750°C) were used.
Catalytic experiments were carried out with H2-N2 gas mixtures containing 800 ppm
NH3 at 700°C and 800°C. Catalyst samples before and after the tests were characterized
with the methods such as temperature programmed reduction (TPR), SEM, N2 isotherm
and XRD. It was shown that there is a certain relationship between aluminum content
of the zeolite and their activity. The possible formation of iron aluminate like clusters
at the reaction temperature was evaluated as one of the reason for the observed poor
activity. It was believed that the aluminum content of the zeolite was determinative in
the size and dispersion of active iron clusters.
References
[1] Jin Hu, Fei Yu, Yongwu Lu, Catalysts (2012) 303-326
[2]J. Zeisler, M. Kleinhappl, H. Hofbauer,
http://bioenergy2020.eu/app/webroot/files/file/Download/ICPS10_paper_Zeisler_final.pdf
[3] Yeliz Durak-Çetin, Alper Sarıoğlan, Şerife Sarıoğlan, Hasancan Okutan, Reac. Kinet. Mech. Cat.,
(2016)
240
Palladium (II) Schiff Base Complexes: Precursor for the
Deposition onto the mesoporous SBA-15 in scCO2 Media
Asım Eğitmena, Bilgehan Güzela
a
Çukurova University, Faculty of Science and Letters, Chemistry Department, 01330 Adana,
TURKEY
Deposition of metals ( Pd,Cu, Ni, Rh, etc. ) on different solid support materials is very
important due to the numerous applications of its composite materials. For catalytic
applications, palladium is the most studied metal due to its versatility. Supported Pd
catalysts are used in reduction and oxidation reactions, hydrogenation, hydrocracking,
carbonylation and other carbon–carbon coupling reactions [1-2].
In this study, Schiff base ligands were synthesized condensation of 2-fluoro-5trifluoromethyl aniline with 2-hydroxy- 4-methyl benzaldehyde and 2-hydroxy5-methyl benzaldehyde. The synthesized schiff bases and their palladium complexes
characterized by elemental analyses, FT-IR, 1H NMR and 13C NMR. In FT-IR spectrum of
ligands specific peaks observed at O-H 3300-3400 C-H(Ar) 3005-3060, C=N 1640-1680,
C-F 1190-1240. Disappearances of O-H peaks at FT-IR spectrum of Pd complexes were
showed the formation of metal complexes and azomethine group shifted to the lower
wavenumbers, 1590-1602 cm-1 in all the complexes suggesting the coordination of the
azomethine nitrogen to the metal centers. This is further substantiated by the presence
of a new band around 450cm-1. The synthesized Palladium complexes were used as
precursor for scCO2 deposition method and characterized by XRD, TEM, SEM and XPS.
The resulting Pd nanoparticles were used as catalyst for Suzuki coupling reaction over
phenyl boronic acid and bromobenzene.
Acknowledges
We would like to thank TUBITAK for financial support (214Z097).
References:
[1] P. Ncube, T. Hlabathe, R. Meijboom, “Palladium Nanoparticles Supported on Mesoporous Silica
as Efficient and Recyclable Heterogenous Nanocatalysts for the Suzuki C–C Coupling Reaction”,
J. Clust Sci 26 (2015) 1873–1888.
[2] C. Erkey, “Prepation of metallic supported nanoparticles and films using supercritical fluid
deposition”, J. of Supercritical Fluids, 47 (2009) 517–522.
241
Synthesis and Characterization of SBA15 Mesoporous Materials
Functionalized with Boron Metal
Taner Tuncera, Gizem Akbıyıka, Tuğba Candaşb,Alime Çıtaka
a
b
Eskişehir Osmangazi University, Department of Chemical Engineering, 26480, Eskişehir.
Bilecik Seyh Edebali University, Chemical and Process Engineering Department, Bilecik.
In a typical synthesis of B-SBA-15 samples which is easily recyclable catalysts has received
increasing attention. Usage of mesoporous materials having adjustable pore size
distribution with a high surface area as catalysts in various reactions is quite common.
As known, the supporting with various metals and chemicals of catalysts affects the
surface activity of the catalyst, thus the yield of the reaction changes. Mesoporous
silica materials (SBAn) due to the large BET surface areas have the better adsorption
properties and provide surface properties, such as acidity and alkalinity can be able
to functionalize with organic groups. Functionalization with metals of mesoporous
materials is a method which is frequently encountered in the literature. Metal loaded
catalysts are used in almost all areas of industry. According to the other mesoporous
materials, SBA15 stands out in terms of larger pore sizes, hydrothermal stability and
having a thicker wall structure. SBA15 which is commonly used in industrial separation,
adsorption, catalysis, sensor, the reactions of solution and gas and in many areas is to
be mainly produced by combining certain proportions of polymer (P123) and silica
(TEOS)[1]. In the literature review, it was found that mesoporous materials supported
boron (B) affect the surface properties. However, boron-loaded SBA15 is less frequently
examined in studies and this also shows that research should be continued over this
subject. In addition to this, considering boron reserves of our country, the synthesis of
the catalyst material which is the main subject of study has been diversified.
In this study, mesoporous SBA-15 materials (B-SBA-15) were synthesized with B content
(Si/B molar ratio 10) by direct hdyrothermal procedure and characterized using BET,
SEM, FT-IR and XRD analysis. According to data obtained from analysis results, all of the
samples have characteristic structure of SBA15.
References:
[1] R. V. Grieken,J.M., Escola,J., Moreno,R., Rodríguez,Chemical Engineering Journal, 155 (2009)
442–450.
242
Determination of ΔH°, ΔS° and ΔG° valuesof B-SBA15
MesoporousMaterials Using InverseGasCromatographyTechnique
Sercan Koça, Tuğçe Günera,AlimeÇıtaka
a
Eskişehir Osmangazi University, Department of Chemical Engineering, 26480, Eskişehir.
According to the other mesoporous materialsSBA-15 stands out in terms of larger
pore sizes, hydrothermal stability and having a thicker wall structure. Recently, for the
production of certain chemicals harm less to the environment, which is easily recyclable
catalysts has receive dincreasingattention. Usage of mesoporous material shaving
adjustable pore size distribution with a high surface area as catalysts in various reactions
is quite common. SBA-15 which is commonly used in industrial separation, adsorption,
catalysis, sensor, the reactions of solution and gas and in many areas is to be mainly
produced by combining certain proportions of polymer (P123) and silica (TEOS). Metal
loaded catalysts are used in almost all areas of industry. In the literature review, it is
found that mesoporous materials supported boron (B) affect the surface properties.
In this study, B-SBA 15 (nSi / nB = 10) synthesized by hydrothermal synthesis method was
used.The inverse gas chromatography (IGC) technique was used in order to determine
the adsorption thermodynamic parameters of the sample.B-SBA-15 sample was used as
filler for the column of the gas chromatography device and was determined adsorption
thermodynamic parameters of unknown properties of B-SBA-15 sample using probe
gas molecules with known properties. According to data obtained from experimental
results, ΔH°, ΔS° and ΔG° values were calculated for all used as a filler B-SBA-15 sample.
References:
[1] Aktaş Ö., Development Of SBA-15 And MCF Supported Catalysts For Selective Oxidation
Reaction Of Propane To Propylene, M.Sc. Thesis, Institute Of Science And Technology,Gazi
University, Ankara, 2008.
243
Single Step Synthesis of HPA loaded Al-PILCs
Suna BALCIa, M.Candan KARAEYVAZa, Gulce ACILa, Funda TURGUT BASOGLUa
a
Gazi University,Engineering Faculty, Maltepe, 06570,ANKARA.
Clay minerals althoughtheir high acidic properties, have restrictions on applications
as catalysts and catalyst support because of small pore size and lack of hydrothermal
stability. Pillaring is one of the effective method used in order to eliminate these
restrictions. By the incorporating of bulky pillars into the clay layers, micro-meso porous
pillared intercalated clay (PILC) with functional surface groups can be obtained.Al Keggin
structure has been used commonly as apillaring agent due toits known chemistry,
thermal stability and acidic properties [1]. Heteropoly acids (HPA) posses high acidic
and redox properties, but they show negative effects such as low surface area and high
solubility in polar mediaon their catalytic applications and these disadvantages can be
eliminated by loading HPAs on porous support [2].
Synthesis of HPA/Al-PILC structure was achieved withthe advantage of similar Keggin
geometry of both Al Keggin cationand HPAanion, using Texas montmorillonite (STx-1)
as host clay. This work which was the first one in the literature was planned by considering
the structural improvements which might be caused by the synergy between cation
and anion.Synthesis of Al-PILC was achieved by using AlCl3 salt, keeping base/metal
(OH/Al) and Al/gram clay ratiosat2.4 and 3.0, respectively. Single step syntheses of HPA/
Al-PILCs were performed by using silicatungstic acid with W/Al ratios of 0.25/1 and 1/1
followed by subsequent calcination at 300 °C. XRD results showed that, pillaring by
aluminum resulted in increase in basal spacing value of clay from 1.54nm to 1.89nm
with no crystal deformation. In the presence of HPA, higher basal spacing values were
obtainedcompared to Al-PILC.Nitrogen adsortion isotherms of all PILCs reflected Type
IV isotherm of the IUPAC classification. BET surface area value of Al-PILC was mesured
as 245 m2/g and small decrease in this value occurred at low HPA loading. Increase of
acid loading quantity caused around 40 % decrease in BET surface area.
References
[1] Adams J. M., McCabe R. W., “Handbook of Clay Science”, Developments in Clay Science, 1,
541-581.
[2] Corma A., “Solid Acid Catalysts”, Current Opinion in Solid State & Mater. Sci., 2, 63-75.
244
Zeolite Catalysis for Bio-oil Upgrading via Esterification
Ayşenur YEŞİLYURTª, Ayşe Gül TÜREª, H. Levent HOŞGÜNª
ªBursa Technical University,Department of Chemical Engineering, 16190, Bursa.
There is a need for alternative fuel sources due to a decrease in oil reserves. One
promising method is conversion of biomass into bio-oil [1]. The chemical composition
of bio-oil obtained from pyrolysis consists of different compounds such as alcohols,
organic acids, ethers, esters, aldehydes, ketones, phenols, etc. It is necessary to upgrade
the bio-oil because of the problems caused by these chemicals. [2] There are numerous
methods for obtained upgrading bio-oil. Among these methods, esterification reaction
with zeolite catalysis is widely used [3-4].
In this study, sulphuric acid modified clinoptilolite and sepiolite samples are used as
catalyst and esterification reaction of acetic acid with ethyl alcohol is selected as model
reaction for bio-oil upgrading. Clinoptilolite samples taken from Gördes, ManisaTURKEY and sepiolite samples taken from Eskisehir-TURKEY. Both zeolites calcined
at 200 °C and 850 °C. Then, all zeolite samples are modified with sulphuric acid.
Esterification reaction of acetic acid with ethyl alcohol was carried out under 65°C
temperature, 500 rpm stirring speed and 1:1 molar ratio of reactants conditions. All
zeolites samples were characterized by N2 adsorption/desorption and XRD.
The results showed that esterification reaction efficiency of sulphuric acid modified
clinoptilolite and sepiolite higher than unmodified clinoptilolite and sepiolite. On
the other hand, calcination also increased the conversion of acetic acid. The highest
conversion of acetic acid was obtained with 200 °C calcined sulphuric acid modified
sepiolite as 42.2%.
References:
[1] P.M. Mortensen, J.-D. Grunwaldt, P.A. Jensen, K.G. Knudsen, A.D. Jensen, A review of catalytic
upgrading of bio-oil to engine fuels, Applied Catalysis A: General, 407, 1–2, 2011, 1–19.
[2] H.B. Goyal, Diptendu Seal, R.C. Saxena, Bio-fuels from thermochemical conversion of renewable
resources: A review, Renewable and Sustainable Energy Reviews, 12, 2, 2008, 504–517.
[3] Liu, Y., Li, Z., Leahy, J. J., Kwapinski, W., Catalytically Upgrading Bio-oil via Esterification,
Energy Fuels, 2015, 29 (6), 3691–3698.
[4] Ciddor, L., Bennett, J. A., Hunns, J. A., Wilson, K., Lee, A. F., Catalytic upgrading of bio-oils by
esterification, Journal of Chemical Technology and Biotechnology, 90, 5, 780–795, 2015
245

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Invited Review Paper FUNCTIONALLY BIOPOLYMER SYSTEMS