Rotating Electrode Methods and Oxygen Reduction Electrocatalysts provides the latest information and methodologies of rotating disk electrode and rotating ring-disk electrode (RDE/RRDE) and oxygen reduction reaction (ORR). It is an ideal reference for undergraduate and graduate students, scientists, and engineers who work in the areas of energy, electrochemistry science and technology, fuel cells, and other electrochemical systems.

Preface xi

Biography xv

List of Contributors xix

Chapter 1 Oxygen Solubility, Diffusion Coefficient, and Solution Viscosity 1

1.1. Introduction 2

1.2. Physical and Chemical Properties of Oxygen 3

      1.2.1. Physical Properties 3

      1.2.2. Chemical Properties 5

1.3. Oxygen Solubility in Aqueous Solutions 5

      1.3.1. Solubility in Pure Water 6

      1.3.2. Electrolyte, Electrolyte Concentration, and pH Effects on O2 Solubility 6

      1.3.3. Temperatu re Effect on O2 Solubility 9

      1.3.4. Pressure Effect on O2 Solubility 9

1.4. O2 Diffusion Coefficients in Aqueous Solution 11

      1.4.1. O2 Diffusion Coefficiencies in Pure Water 13

      1.4.2. Electrolyte and Electrolyte Concentration Effects on O2 Diffusion Coefficient 15

      1.4.3. Temperature Effect on O2 Diffusion Coefficient 17

      1.4.4. Pressure Effect on O2 Diffusion Coefficient 17

1.5. Viscosity of Aqueous Solution 18

      1.5.1. Viscosity of Pure Wate r 19

      1.5.2. Electrolyte, Electrolyte Concentration, and pH Effects on Viscosity 19

      1.5.3. Temperature Effect on Viscosity 22

      1.5.4. Pressure Effect on Viscosity. 24

1.6. Oxygen Solubility and Diffusion Coefficient in Nation③ Membranes 24

      1.6.1. Temperature Effect on both the O2 Solubility and Diffusion Coefficient 25

      1.6.2. Pressure Effect on both the O2 Solubility and Diffusion Coefficient 25

      1.6.3. Water Content Effect on both the O2 Solubility and Diffusion Coefficient 25

1.7. Chapter Summary 28

References 29

Chapter 2 Electrode Kinetics of Electron-Transfer Reaction and Reactant Transport in Electrolyte Solution 33

2.1. Introduction 34

2.2. Kinetics of Electrode Electron-Transfer Reaction 34

      2.2.1. Fundamental Chemical Reaction Kinetics 34

      2.2.2. Fundamentals of Electrode Reactions (Bulter-Volmer Equation) 35

2.3. Kinetics of Reactant Mass Transpo rt Near Electrode Surface 44

      2.3.1. Three Types of Reactant Transpo rt in Electrolyte (Diffusion, Convection, and Migration) 45

      2.3.2. Nonsteady-State Diffusion Process of Reactant when the Electro！叭e Solution at the Static State 48

      2.3.3. Steady State Diffusion-Convection Process of Reactant 54

2.4. Effect of Reactant Transport on the Electrode Kinetics of Electron-Transfer Reaction 57

      2.4.1. Effect of Reactant Transpo rt on the Kinetics of Electron-Transfer Process 57

      2.4.2. Effect of Reactant Transport on the Thermodynamics of Electrode Reaction 59

2.5. Kinetics of Reactant Transpo同 Near and within Porous Matrix Electrode Layer 61

2.6. Chapter Summary 64

References 64

Chapter 3 Electrocatalysts and Catalyst Layers for Oxygen

Reduction Reaction 67

3.1. Introduction 68

3.2. Concepts of Catalytic Activity and Stability 69

      3.2.1. Catalyst and Catalytic Reaction 70

      3.2.2. Catalytic Activity 70

      3.2.3. Electrocatalytic Activity Cata Iytic TOF and Current Density 72

      3.2.4. Electrocatalytic Activity Onset Potential and Half-wave Potential 76

      3.2.5. Stability of Electrocatalysts 77

      3.2.6. Composition and Structure of ORR Electrocatalysts 77

      3.2.7. Requirements for ORR Electrocatalyst 81

3.3. Current Research Effort in ORR Electrocatalysis 87

      3.3.1. Noble Metal-based Electrocatalysts 87

      3.3.2. Non-noble Metal-based ORR Electrocatalysts 89

3.4. Electrocatalysts Synthesis and Characterization 92

      3.4.1 Synthesis Methods for ORR Electrocatalysts 93

      3.4.2. Characte rization of ORR Electrocatalysts 99

3.5. Catalyst Layers, Fabrication, and Characterization 106

      3.5.1. Introduction to ORR Catalysts Layer 106

      3.5.2. Catalyst Layer Fabrication and Characterization 110

      3.5.3. Catalyst Layer Characterization 117

3.6. Chapter Summary 122

References 123

Chapter 4 Electrochemi cal Oxygen Reduction Reaction 133

4.1. Introduction 134

4.2. Electrochemical Thermodynamics and Electrode Potential of ORR 134

4.3. Electrochemical Kinetics and Mechanism of ORR 137

      4.3.1. ORR on Platinum Catalyst 137

      4.3.2. ORR on Pt alloys 144

      4.3.3. Difference in ORR Activity Catalyzed by Pt, Pt-Skeleton, and Pt-Skin Surfaces 145

4.4. ORR on Carbon Materials 147

      4.4.1. ORR on Graphite and Glassy Carbon 148

      4.4.2. ORR on Carbon Nanotubes 151

      4.4.3. ORR on Heteroatom-Doped Carbons 152

      4.4.4. ORR on Pretreated Carbon Surface 152

      4.4.5. ORR on Graphene 154

4.5. ORR on Macrocyclic Transition Metal Complexes 155

4.6. Fundamental Understanding of ORR Mechanisms 160

4.7. Importance of ORR in Fuel Cells 165

4.8. Chapter Summa ry 166

References 166

Chapter 5 Rotating Disk Electrode Method 171

5.1. Introduction 172

5.2. Rotating Disk Electrode Theory 172

      5.2.1. Diffusion-Convection Layer Near the Electrode Surface 173

      5.2.2. Current Densities of Rotating Disk Electrode 175

      5.2.3. Koutecky Levich Equation 180

5.3. Experimental Measurements of Rotating Disk Electrode 184

      5.3.1. Rotating Disk Electrode Apparatus 184

      5.3.2. Electrochemical Cells for RDE Measurements 185

      5.3.3. Working Electrode Preparation 187

      5.3.4. Measurement for Electrochemical Activity of the Catalysts 189

      5.3.5. Recording ORR Cyclic Voltammograms 192

      5.3.6. Recording ORR Current-Potential Curves Using RDE Technique 193

      5.3.7. Analysis of ORR Current-Potential Data 193

      5.3.8. Cautions When Using RDE Technique 195

5.4. Chapter Summary 197

References 198

Chapter 6 Rotating Ring-Disk Electrode Method 199

6.1. Introduction 199

6.2. Theory of Rotating Ring-Disk Electrode Technique 200

      6.2.1. Electrochemical Reaction on the Disk Electrode 201

      6.2.2. Electrochemical Reaction on the Ring Electrode 203

6.3. RRDE Collection Efficiency 205

6.4. RRDE Instrumentation 210

6.5. RRDE Measurements 213

6.6. RRDE Data Analysis for ORR 215

      6.6.1. Proposed ORR Mechanisms and Their Analys is Based on the RRDE Data 216

      6.6.2. ORR Apparent Electron-Transfer Number and the Formed Percentage of Peroxide Measured by RRDE Technique 221

6.7. Chapter Summary 228

References 228

Chapter 7 Appl ications of RDE and RRDE Methods in Oxygen Reduction Reaction 231

7.1. Introduction 232

7.2. RDE/RRDE Study for ORR on Pt-based Electrode Surfaces 232

      7.2.1. Oxygen Reduction Reaction on Crystal Pt-Facet Electrode Surfaces 232

      7.2.2. Oxygen Reduction Reaction on Polycrystalline Pt Surface 235

      7.2.3. Oxygen Reduction Reaction on Pt Monolayer Coated on Other Metal Electrode Surfaces. . 236

7.3. RDE/RRDE Study for ORR on Carbon-Based Electrode Surfaces 240

7.4. Oxygen Reduction Reaction on Monolayer Substances-Modified Carbon Electrode Surfaces 245

      7.4.1. ORR on Anthraquinone-Modified Carbon Electrodes 245

      7.4.2. ORR on Metal Macrocycle Complex-Coated Carbon Electrodes 248

7.5. RDE/RRDE Study for ORR on the Surfaces of Supparted Pt Particle- and Pt Allay Particle-Based Catalyst Layer 255

      7.5.1. ORR on the Surfaces of Pt-Based Catalyst Layer 257

      7.5.2. ORR on the Surfaces of Pt Alloy Based Catalyst Layer 257

7.6. RDE/RRDE Study for ORR on the Surfaces of Non-Noble Metal Catalyst Layer 265

7.7. Chapter Summary 273

References 273

lndex 279

Dr. Jiujun Zhang is a Principal Research Officer and Fuel Cell Catalysis Core Competency Leader at the National Research Council of Canada (NRC) Institute for Fuel Cell Innovation (NRC-IFCI, now changed to Energy, Mining & Environment Portfolio (NRC-EME)). Dr. Zhang received his BS and MSc in Electrochemistry from Peking University in 1982 and 1985, respectively, and his PhD in Electrochemistry from Wuhan University in 1988. After completing his PhD, he took a position as an associate professor at the Huazhong Normal University for 2 years. Starting in 1990, he carried out three terms of postdoctoral research at the California Institute of Technology, York University, and the University of British Columbia. Dr. Zhang has over 30 years of R&D experience in theoretical and applied electrochemistry, including over 15 years of fuel cell R&D (among these 6 years at Ballard Power Systems and 10 years at RC), and 3 years of electrochemical sensor experience. Dr. Zhang holds several adjunct professorships, including one at the University of Waterloo, one at the University of British Columbia, and one at Peking University. Up to now, Dr. Zhang has coauthored more than 300 publications including over 200 refereed journal papers with approximately 6200 citations, 11 edited/ coauthored books, 11 conference proceeding papers, 12 book chapters, as well as 50 conference and invited oral presentations. He also holds over 10 US/EU/WO/JP/CA patents, 9 US patent publications, and produced in excess of 80 industrial technical reports. Dr. Zhang serves as the editor/editorial board member for several international journals as well as Chief-in-Editor for book series (Electrochemical Energy Storage and Conversion, CRC press). Dr. Zhang is an active member of The Electrochemical Society, the International Society of Electrochemistry, and the American Chemical Society.

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