《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》

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《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》
用于醇 - 直接氧化燃料电池的催化剂
编辑：
Zhen-Xing Liang
South China University of Technology, Guangzhou, China
Tim S. Zhao
The Hong Kong University of Science and Technology, Hong Kong
出版社：RSC
出版时间：2012年

《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》

《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》

《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》

《Catalysts for Alcohol-FuelledDirect Oxidation Fuel Cells》

目录
Chapter 1 Electrocatalysis of Alcohol Oxidation Reactions at Platinum
Group Metals 1
Claude Lamy and Christophe Coutanceau
1.1 Introduction 1
1.2 Thermodynamics and Kinetics of Alcohol Oxidation
Reactions 2
1.2.1 Thermodynamic Data 2
1.2.2 Kinetics Problems 6
1.3 Preparation and Physicochemical Characterization of
Platinum-Based Nanocatalysts 7
1.3.1 Synthesis by Chemical Methods 8
1.3.2 Synthesis by Electrochemical Deposition 10
1.3.3 Synthesis by Plasma-Enhanced PVD 11
1.3.4 Physicochemical Characterizations 11
1.4 Experimental Methods for the Elucidation of Reaction
Mechanisms 12
1.4.1 Cyclic Voltammetry and CO Stripping 12
1.4.2 Infrared Reflectance Spectroscopy 12
1.4.3 Differential Electrochemical Mass
Spectrometry 14
1.4.4 Chromatographic Techniques 14
1.5 Main Parameters of the Electrode Material Controlling
the Electro-reactivity of Alcohols 15
1.5.1 Chemical Nature of the Electrode Material 15
1.5.2 Effect of Crystallographic Structure 15
1.5.3 Modification of the Electrode Properties by
Metal Adatoms 17
1.5.4 Binary and Multimetallic Electrodes 17
RSC Energy and Environment Series No. 6
Catalysts for Alcohol-Fuelled Direct Oxidation Fuel Cells
Edited by Zhen-Xing Liang and Tim S. Zhao
# The Royal Society of Chemistry 2012
Published by the Royal Society of Chemistry, www.rsc.org
vii
1.5.5 Effect of the Particle Size and Carbon Support 18
1.5.6 Platinum-Based Nanoparticles and
Nanocrystals 19
1.6 Survey of the Results on the Electro-oxidation of
Several Alcohols 20
1.6.1 The Electro-oxidation of Methanol 21
1.6.2 The electro-oxidation of Ethanol 31
1.6.3 The Electro-oxidation of Polyols 48
1.7 Summary 64
References 65
Chapter 2 Nanoalloy Electrocatalysts for Alcohol Oxidation Reactions 71
Jun Yin, Bridgid Wanjala, Bin Fang, Jin Luo, Rameshowri
Loukrakpam, Lefu Yang, Shiyao Shan, Ming Nie and Chuan-
Jian Zhong
2.1 Introduction 71
2.2 Preparation of Nanoalloy Catalysts 75
2.3 Electrocatalytic Activity of Bimetallic Catalysts 77
2.3.1 AuPt Alloy and Core–Shell Nanoparticle
Catalysts 77
2.3.2 PdCo Alloy Nanoparticle Catalysts 82
2.4 Phase and Surface Properties of Bimetallic
Nanoparticle Catalysts 83
2.4.1 Bimetallic Phase Properties 83
2.4.2 Bimetallic Surface Properties 88
2.5 Summary 91
Acknowledgements 91
References 91
Chapter 3 Theoretical Studies of Formic Acid Oxidation 97
Wang Gao and Timo Jacob
3.1 Introduction 97
3.2 Methods 100
3.3 Results and Discussion 101
3.3.1 Gas-Phase Reaction 101
3.3.2 Influence of Water Solvation 105
3.3.3 Eley2Rideal Mechanisms 108
3.3.4 Kinetics Analysis 112
3.3.5 Role of Co-adsorbed CO and OH 114
3.4 Summary 125
Acknowledgements 125
References 126
viii Contents
Chapter 4 Gold Leaf Based Electrocatalysts 129
Rongyue Wang and Yi Ding
4.1 Introduction 129
4.2 Nanoporous Gold Leaf 131
4.2.1 History and Formation Mechanism of NPG 131
4.2.2 Structural Properties of NPG Leaf 133
4.2.3 Electrocatalysis of NPG Leaf 135
4.3 Platinum-Plated Nanoporous Gold Leaf 137
4.3.1 Plating Methods 138
4.3.2 Structure and Stability of Pt-NPG Leaf 141
4.3.3 Electrocatalysis of Pt-NPG Leaf 144
4.3.4 Fuel Cell Performance of Pt-NPG Leaf 147
4.4 NPG-Based Electrocatalysts for Formic Acid
Oxidation 150
4.5 Summary 154
Acknowledgements 155
References 155
Chapter 5 Nanocatalysts for Direct Borohydride Oxidation in Alkaline
Media 158
Christophe Coutanceau, Ste`ve Baranton and Ma´rio Simo˜esg
5.1 Introduction 158
5.2 Thermodynamics and Mechanism of Sodium
Borohydride Oxidation 160
5.3 Experimental Details 167
5.3.1 Materials 167
5.3.2 Synthesis of Catalysts by the ‘‘Water-in-Oil’’
Microemulsion Method 169
5.3.3 Electrochemical Measurements 170
5.3.4 TEM, XRD and XPS Characterization Methods 170
5.4 Characterization of the Nanocatalysts 171
5.5 Evaluation of the Catalytic Activity and Selectivity
towards Sodium Borohydride Electro-oxidation 177
5.5.1 Electrochemical Methods 177
5.5.2 Evaluation of the BOR on Monometallic
Nanocatalysts 181
5.5.3 Evaluation of the BOR on Pd-Based Bimetallic
Catalysts 188
5.5.4 Evaluation of the BOR on Pt-Based
Multimetallic Catalysts 196
5.6 Summary 199
Acknowledgements 201
References 201
Contents ix
Chapter 6 Bioelectrocatalysis in Direct Alcohol Fuel Cells 206
H. A. Reeve and K. A. Vincent
6.1 Introduction 206
6.1.1 Opportunities for Enzymes at the Anode of Fuel
Cells 208
6.1.2 Opportunities for Enzymes at the Cathode of
Fuel Cells 211
6.1.3 Limitations in Assembling Energy Devices with
Enzymes 211
6.2 Strategies for Wiring Enzyme Electrocatalysts to Electrodes 212
6.2.1 Cofactor Supply to NAD(P)+-Dependent
Dehydrogenases 213
6.2.2 Redox Hydrogels 214
6.2.3 Tethers or Conductive Linkers 214
6.2.4 Direct Electron Transfer 216
6.2.5 Wiring Whole Cells for Microbial Fuel Cells:
Mediated and Direct Electron Transfer 218
6.3 Examples of Enzyme Electrocatalysis 218
6.3.1 Methanol and Ethanol 219
6.3.2 Sugars and Carbohydrates 220
6.3.3 Glycerol 222
6.4 Microbial Fuel Cells 222
6.5 Summary 223
Acknowledgements 223
References 223
Chapter 7 Challenges and Perspectives of Nanocatalysts in
Alcohol-Fuelled Direct Oxidation Fuel Cells 227
E. H. Yu, X. Wang, X. T. Liu and L. Li
7.1 Challenges with Current Direct Oxidation Fuel Cell
Catalysts 227
7.1.1 CO Poisoning 228
7.1.2 Oxygen Reduction Catalysts 230
7.1.3 Carbon Corrosion 230
7.1.4 Platinum Dissolution and Growth 232
7.1.5 Ruthenium Dissolution 233
7.2 Approaches to Catalyst Performance Enhancement 233
7.2.1 Development of Composite Catalysts with Noble
Metals 233
7.2.2 Novel CarbonMaterials asCatalysts and Substrates 240
7.2.3 Non-carbon-Based Catalyst Substrates 242
7.3 Summary 244
References 244
Subject Index 250

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