Advanced Electrocatalysts for Low-Temperature Fuel Cells (eBook)

Prof. Dr. Francisco Javier Rodríguez-Varela is Full Professor at the Center for Research and Advanced Studies (Cinvestav), Saltillo Campus, Mexico. He obtained his Master degree in Solar Energy from the National University of Mexico (UNAM) in 1998, and his PhD in Metallurgical Engineering and Electrochemistry from École Polytechnique de Montréal (Canada) in 2004. His PhD thesis focused on the development of anode electrocatalysts for Direct Propane Fuel Cells. Then, he joined the Chemical Engineering Department of École Polytechnique de Montréal as a post-doctoral fellow (2004-2005). Since January of 2006, Dr. Rodríguez-Varela is a Researcher at Cinvestav Saltillo Campus (Full Professor since 2009). At Cinvestav, he has worked in the development and characterization of nanostructured anode and cathode electrocatalysts for PEMFCs, DAFCs and MFCs. He has served as President of the Mexican Hydrogen Society (2012-2014) and Coordinator of the Mexican Hydrogen Network (2015). Member of the Scientific Committee of Journal of New Materials for Electrochemical Systems (2007-to date) and Guest Editor of the same journal (2008-2013). Guest Editor of Journal of Applied Electrochemistry (2015). Dr. Rodríguez-Varela has been Principal Investigator of several national research projects and two bilateral international projects with China and India, funded by the Mexican National Council for Science and Technology (CONACyT).Prof. Dr. Teko W. Napporn is a tenured researcher of French National Center of Scientific Research (CNRS), working at  the Poitiers Institute of Materials and Environmental chemistry (IC2MP). He received his Master's degree in Applied Chemistry in 1991, and his PhD in Electrochemistry in 1997 from the University of Poitiers (France). During his PhD thesis, he developed anode materials for direct methanol fuel cell. After his PhD, he joined the Electrocatalysis group at University of São Paulo at São Carlos, Brazil, as a post-doctoral fellow and later in 1999, the École Polytechnique de Montreal (Canada) as research associate. There, he had studied and developed the single chamber SOFC system in collaboration with Hydro-Quebec. Since 2008 he got a tenure position at CNRS for developing novel nanomaterials for electrocatalysis especially for application in energy conversion and storage systems. His recent research topics are focused on (i) morphology and size controlled nanomaterials as novel electrodes for fuel cell and water electrolyzer (acid and alkaline media); (ii) oxygen reduction reaction and oxygen evolution reaction; (iii) full porous single chamber SOFC. Since September 2015, he is Adjunct professor at the Chemistry of Hydrogen energy conversion unit of the Institute of Advanced Science of Yokohama National University in Japan.

Contents 5
About the Authors 7
Chapter 1: Introduction: Low-Temperature Fuel Cells 20
1.1 Introduction 21
1.2 Electrocatalytic Reactions in Anion Exchange Membrane Fuel Cells (AEMFCs) 21
1.2.1 H2/O2 AEMFCs 22
1.2.2 Direct Methanol AEMFCs (DM-AEMFCs) 24
1.2.3 Direct Ethanol AEMFCs (DE-AEMFCs) 24
1.2.4 Direct Ethylene Glycol AEMFCs (DEG-AEMFCs) 25
1.2.5 Direct Glycerol AEMFCs (DG-AEMFCs) 26
1.2.6 AEMFCs Operating with Other Fuels 27
1.3 Performance of Several Types of Nanostructured Anodes and Cathodes in AEMFCs 28
1.4 Advances in Membranes for PEM and AEM Fuel Cells 33
1.4.1 Proton Exchange Membranes (PEMs) 34
1.4.2 Anion Exchange Membranes (AEMs) 44
1.5 Electrocatalytic Reactions in Proton Exchange Membrane (PEM) Fuel Cells 48
1.5.1 Reactions of Fuel at the Anode of PEMFCs 49
1.5.1.1 Case of H2 49
1.5.1.2 Case of CH3OH 51
1.5.1.3 Case of CH3CH2OH 52
1.5.1.4 Reaction at the Cathode: Oxygen Reduction Reaction (ORR) 52
1.6 Performance of New Class of Electrode Materials for Proton Exchange Membrane (PEM) Fuel Cells 56
1.7 Conclusion 58
References 58
Chapter 2: Recent Advances on Electrocatalysts for PEM and AEM Fuel Cells 69
2.1 Introduction 70
2.2 Hydrogen Oxidation Reaction 70
2.2.1 Electrode Materials for Hydrogen Oxidation Reaction in Acidic Media 73
2.2.1.1 Pt-Based Alloys 74
2.2.1.2 Pt-Metal Oxide 76
2.2.1.3 Core-Shell Architectures 77
2.2.1.4 Pt/Transition Metal Carbides and Nitrides 80
2.3 Oxygen Reduction Reaction 80
2.3.1 Introduction and Reaction Mechanism 80
2.3.2 Strategies to Improve the Platinum Performance for the ORR 84
2.3.2.1 Morphological Effects on Platinum Electrocatalysts 84
2.3.2.2 Alloying 85
Pt-Late Transition Metal Alloys 86
Pt-Early Transition Metal and Lanthanide Alloys 88
2.3.2.3 Core-Shell Structures 89
2.3.3 Non-Platinum Electrocatalysts 90
2.3.3.1 Palladium and Palladium-Alloy Catalysts 90
2.3.4 Stability Issues 91
2.4 Conclusions 93
References 93
Chapter 3: Electrocatalysis of Alternative Liquid Fuels for PEM Direct Oxidation Fuel Cells 108
3.1 Introduction 109
3.2 Direct Methanol Fuel Cell (DMFC) 110
3.2.1 Methanol Crossover 111
3.2.2 Methanol Oxidation Reaction (MOR) 112
3.2.3 Catalysts for Methanol Oxidation Reaction 113
3.2.4 Performance of Direct Methanol Fuel Cell (DMFC) 115
3.3 Direct Ethanol Fuel Cell 118
3.3.1 Ethanol Oxidation Reaction (EOR) 119
3.3.2 Ethanol Crossover 121
3.3.3 Catalyst for Ethanol Oxidation Reaction (EOR) 121
3.3.4 Performance of Direct Ethanol Fuel Cell (DEFC) 123
3.4 Direct Ethylene Glycol Fuel Cell (DEGFC) 124
3.4.1 Ethylene Glycol Oxidation Reaction 125
3.4.2 Catalyst for Ethylene Glycol Oxidation Reaction (EGOR) 126
3.4.3 Performance of Direct Ethylene Glycol Fuel Cell (DEGFC) 127
3.5 Direct Formic Acid Fuel Cell 128
3.5.1 Reaction Mechanism 129
3.5.2 Catalyst for Formic Acid Electro-Oxidation 130
3.5.3 Cell Configuration and Performance 132
3.6 Direct Glycerol Fuel Cell (DGEFC) 133
3.7 Conclusions and Outlook 135
References 137
Chapter 4: Overview of Direct Liquid Oxidation Fuel Cells and its Application as Micro-Fuel Cells 146
4.1 Introduction 147
4.2 Overview of Fabrication Technologies for Micro-Fuel Cells 147
4.3 Direct Liquid Fuel Cell (DLFC) Designs 149
4.3.1 Proton Exchange Membrane Direct Liquid Fuel Cell (PEM-DLFC) 149
4.3.2 Membraneless Microfluidic Direct Liquid Fuel Cell (MF-DLFC) 150
4.3.3 Mixed-Reactant Membraneless Direct Liquid Fuel Cell (MR-DLFC) 150
4.4 Oxygen Reduction Reaction (ORR) 151
4.5 Methanol Oxidation Reaction (MOR) 152
4.5.1 Catalysis in Acid Media 153
4.5.2 Catalysis in Alkaline Media 153
4.5.3 Micro-Direct Methanol Fuel Cells (?DMFC) 154
4.6 Ethanol Oxidation Reaction (EOR) 162
4.7 Formic Acid Oxidation Reaction (FAOR) 168
4.8 Ethylene Glycol Oxidation Reaction (EGOR) 171
4.9 Glycerol Oxidation Reaction (GlyOR) 173
4.10 Glucose Oxidation Reaction (GOR) 173
4.11 Future Prospects 178
4.12 Acknowledgements 179
References 180
Chapter 5: Application of Novel Carbonaceous Materials as Support for Fuel Cell Electrocatalysts 192
5.1 Introduction 192
5.2 Graphene 194
5.2.1 Synthesis Techniques 194
5.2.2 Application as Support and Dispersion of Metal Nanoparticles 199
5.3 Ordered Mesoporous Carbons 202
5.3.1 Synthesis of OMCs 202
5.3.2 Surface Functionalization of OMCs 209
5.3.3 Application of OMCs as Support for Metal Catalysts 210
5.4 Green Carbons 212
5.4.1 Biomass as Source of Novel Carbons 213
5.4.2 New Family of Green Carbon Supports 216
5.4.3 Anchorage of Nanoparticles on Green Carbons 218
5.5 Conclusions and Outlook 220
References 221
Chapter 6: Progress on the Functionalization of Carbon Nanostructures for Fuel Cell Electrocatalysts 231
6.1 Introduction 232
6.2 Covalent Functionalization 235
6.2.1 =O, -OH, -COOH Functionalization 235
6.2.2 Nitrogen Functionalization 237
6.3 Non-covalent Functionalization 241
6.3.1 Surface Defects 241
6.3.2 Surfactant-Based Non-Covalent Functionalizing Carbon Support 241
6.3.3 Polymer-Based Non-Covalent Functionalizing Carbon Support 244
References 246
Chapter 7: Non-Noble Metal Electrocatalysts for the Oxygen Reduction Reaction in Fuel Cells 251
7.1 Introduction 252
7.2 Fundamentals of the ORR 252
7.3 Electrocatalysts for ORR in Acid Media 256
7.3.1 Transition Metal Macrocycles 256
7.3.2 Transition Metal Chalcogenides 258
7.3.3 Transition Metal Nitrides and Carbides 260
7.4 Electrocatalysts for ORR in Alkaline Media 261
7.4.1 Perovskite-Type Oxides 261
7.4.2 Spinel-Type Oxides 264
7.4.3 Heteroatom-Doped Carbon Materials 266
7.5 Conclusions 270
References 270
Chapter 8: Non-Noble Metal as Catalysts for Alcohol Electro-oxidation Reaction 279
8.1 Introduction 280
8.1.1 Methanol 281
8.1.2 Ethanol 281
8.1.3 Ethylene Glycol 282
8.1.4 Non-Noble Metals as Catalysts for Alcohol Electrooxidation Reaction 282
8.2 Methanol Oxidation Reaction (MOR) on Nickel-Based Anodes 283
8.2.1 Effect of Methanol Concentration 286
8.2.2 Binary and Ternary Nickel-Based Catalyst for Methanol Oxidation 286
8.2.3 Effect of Method of Synthesis 290
8.2.4 Methanol Oxidation Reaction on Other Non-Noble Metal-Based Catalysts 290
8.3 Ethanol Oxidation Reaction (EOR) on Non-noble Metals 294
8.3.1 Nickel-Based Anodes 294
8.3.2 Iridium-Based Anodes 295
8.3.3 Cobalt-Based Anodes 299
8.4 Ethylene Glycol Oxidation (EGOR) in Alkaline Media 300
8.4.1 HYPERMEC (Fe-Co-Ni/C) 301
8.5 Conclusions 301
References 301
Index 307