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Non-oxide electrocatalysts for energy-saving hybrid water electrolysis systems
Replacing thermodynamically unfavorable oxygen evolution with small molecule oxidation can reduce the energy input of water electrolysis while co-producing value-added chemicals. Hybrid Water Electrolysis: Non-Oxide Electrocatalysts in Small Molecule Oxidation, written by a team of electrochemistry and catalysis researchers from four countries, provides detailed coverage of functional electrocatalysts -- metal sulfides, carbides, nitrides, phosphides, and single atom catalysts --applied to this coupled approach.
The book examines nanostructured electrocatalytic materials developed via pulsed laser techniques and their deployment in hybrid electrolyzers for hydrogen fuel production alongside oxidation of benzyl alcohol, methanol, ethanol, urea, hydrazine, furfural, and formic acid. Coverage includes reaction mechanisms, governing principles for catalytic behavior, stability analysis, and an assessment of challenges and opportunities for scaling these systems to industrial application.
Readers will also find:
Detailed discussion of metal sulfide, carbide, nitride, and phosphide electrocatalysts and their catalytic mechanisms in small molecule oxidation reactions
Case studies illustrating how hybrid electrolyzer configurations simultaneously produce hydrogen fuel and value-added chemical products at reduced energy cost
Analysis of single atom catalysts and their role in enhancing selectivity and activity for coupled electrolysis processes
Coverage of pulsed laser synthesis techniques for fabricating nanostructured electrocatalytic materials with controlled morphology and composition
Assessment of scale-up challenges and industrial opportunities for transitioning hybrid water electrolysis from laboratory to commercial deployment
Designed for catalytic chemists, surface chemists, physical chemists, inorganic chemists, and chemical engineers, this reference delivers the mechanistic detail and materials science coverage required to advance non-oxide electrocatalyst development for hybrid water electrolysis and sustainable hydrogen production.
Contents
List of Contributors xv
About the Editors xxi
Preface xxiii
Part I Fundamental 1
1 Fundamentals and Advantages of Hybrid Water Electrolysis 3
Vipada Aupama, Phonnapha Tangthuam, Ahmad Azmin Mohamad, and Soorathep Kheawhom
1.1 Concept and Scope 3
1.2 Thermodynamic and Kinetic Basis for Energy Reduction 7
1.3 Anodic Reaction Space and Substrate Selection 9
1.4 Advantages Beyond Voltage: Coproduction, Safety, and Sustainability 13
1.4.1 Coproduction: Transforming the Anode into a Chemical Manufacturing Module 14
1.4.2 Safety and Operational Flexibility: Reducing Oxygen-related Constraints 14
1.4.3 Sustainability and Circularity: Coupling Hydrogen with Waste Conversion 15
1.4.4 Interdependence of Advantages and the Role of System-level Metrics 16
1.5 Remaining Challenges and Outlook 16
References 19
Part II Alcohol-assisted Water Electrolysis 23
2 Metal Carbides and Nitrides Electrocatalysts for Alcohol-assisted Water Electrolysis 25
Phonnapha Tangthuam, Vipada Aupama, Ahmad Azmin Mohamad, and Soorathep Kheawhom
2.1 Background and Scope 25
2.2 Intrinsic Properties Governing Electrocatalytic Activity 27
2.3 Catalytic Roles in Alcohol-assisted Electrolysis Systems 29
2.3.1 Cathode: HER 30
2.3.2 Anode: AOR 30
2.4 Surface Dynamics and Stability Under Operating Conditions 31
2.4.1 Surface Reconstruction as Activation and Degradation 32
2.4.2 Oxidation, Corrosion, and the Conductive-core/Active-shell Picture 33
2.4.3 Adsorbate-driven Effects and Selectivity Drift 33
2.4.4 Defects, Vacancies, and Stability-Activity Trade-offs 34
2.4.5 Electrode-level Stability 34
2.4.6 Assessing Stability in Hybrid Electrolysis 34
2.4.7 Design Implications 35
2.5 Reaction Pathways and Product Selectivity in Alcohol Oxidation 35
2.5.1 Elementary Steps and Pathway Competition 35
2.5.2 Adsorption Energetics as a Selectivity Lever 36
2.5.3 Surface Oxygenated Species and Reconstructed States 36
2.5.4 Poisoning, Carbon Balance, and Long-term Selectivity 36
2.5.5 Multicomponent Carbides and Nitrides in Selectivity Tuning 37
2.5.6 Selectivity Metrics and Benchmarking 37
2.6 Engineering Strategies to Enhance Performance 37
2.6.1 Nanostructuring and Hierarchical Porosity 38
2.6.2 Morphology and Surface Termination Control 39
2.6.3 Defect and Vacancy Engineering 39
2.6.4 Heteroatom Doping 39
2.6.5 Multicomponent Carbides and Nitrides 39
2.6.6 Heterostructures and Interfaces 40
2.6.7 Conductive Scaffolds and Self-supported Electrodes 40
2.6.8 Electrode Architecture and Transport 40
2.6.9 Benchmarking During Engineering Optimization 40
2.7 Comparative Summary of Carbides vs. Nitrides 40
2.8 Outlook and Remaining Challenges 41
References 44
3 Single-atom Electrocatalysts for Alcohol-assisted Water Electrolysis 47
P. Keerthana, Soorya S. Raj, and M. L. Aruna Kumari
3.1 Introduction 47
3.2 Fundamentals of AAWE 49
3.2.1 Methanol-assisted Hydrogen Production 50
3.2.2 Ethanol-assisted Hydrogen Production 51
3.2.3 Propanol-assisted Hydrogen Production 52
3.2.4 Glycerol-assisted Hydrogen Production 52
3.3 SAECs: Concept and Design Principles 53
3.3.1 NM-SACs 54
3.3.2 SACs@ATMs 55
3.4 Synthesis Strategies of SAECs 58
3.4.1 Bottom-up Methods 58
3.4.1.1 Atomic Layer Deposition Method 58
3.4.1.2 Electrodeposition Method 59
3.4.1.3 Pyrolysis-assisted Method 60
3.4.1.4 Wet-chemical Synthesis 61
3.4.2 Top-down Method 62
3.5 Integration of SAECs into AAWE 63
3.6 Challenges and Perspectives 67
3.7 Conclusion 69
References 69
4 Metal Alloys Electrocatalysts for Alcohol-assisted Water Electrolysis 81
Rafael M. P. Araujo, Sidney C. Z. Costa, M. Janete Giz, and Giuseppe A. Camara
4.1 Fundamentals of Water Electrolysis 81
4.2 Hybrid Water Electrolysis 82
4.3 Alcohol-assisted Water Electrolysis 82
4.4 Metal Alloys for Alcohol Electrooxidation 83
4.5 Metal Alloys for Hydrogen Evolution Reaction 88
4.6 Summary of the Current Landscape 89
References 90
5 Metal Borides and Selenides for Alcohol-assisted Water Electrolysis 95
Yogapriya Selvaraj, Senthilkumar Nangan, Kiruthika Paramasivam, Anbazhagan Venkattappan, Vijayakumar Elayappan, and Soorathep Kheawhom
5.1 Introduction 95
5.2 Electrochemical Reactions Involved in OER, HER, and Alcohol Oxidation Reaction at Electrode Material 97
5.2.1 Mechanism of OER 97
5.2.2 Mechanism of HER 98
5.2.3 Mechanism of Alcohol Oxidation Reaction 99
5.3 Electrocatalytic Performance in Alcohol-assisted Electrolysis in Metal Borides and Selenides 100
5.3.1 Significance of HER 100
5.3.2 HER Activity of Borides and Selenides 101
5.3.2.1 HER Activity of Borides 101
5.3.2.2 HER Activity of Selenides 102
5.3.3 Synergistic Effects in Bimetallic or Hybrid Systems 104
5.4 Tafel Slope, Onset Potential, and Overpotential 105
5.4.1 Tafel Slope 105
5.4.2 Onset Potential 105
5.4.3 Overpotential 106
5.5 Alcohol Oxidation Reaction Mechanism of Ethanol, Methanol, and Glycerol Oxidation 107
5.5.1 Ethanol Oxidation 107
5.5.2 Methanol Oxidation 108
5.5.3 Glycerol Oxidation 110
5.5.4 Borides and Selenides as Anodic Catalysts 112
5.5.5 Selectivity and Product Distribution 114
5.5.6 Overall Electrolysis Performance 116
5.6 Challenges and Future Perspective 116
5.7 Conclusion 117
Acknowledgments 118
References 118
6 Non-oxide Electrocatalysts for Glycerol Oxidation-coupled Water Electrolysis 127
Phonnapha Tangthuam, Vipada Aupama, and Soorathep Kheawhom
6.1 Introduction and Scope 127
6.2 Fundamentals of Glycerol Oxidation in Hybrid Electrolysis 129
6.2.1 Thermodynamic Comparison of OER and Glycerol Oxidation 130
6.2.2 Glycerol Oxidation Reaction Network 131
6.2.3 Performance Metrics for Glycerol-assisted Electrolysis 131
6.3 Non-oxide Electrocatalyst Families and Design Strategies for Glycerol Oxidation 132
6.3.1 Comparative Overview Under Glycerol Oxidation Conditions 132
6.3.2 Design Motifs Across Non-oxide Families 135
6.4 Mechanistic Insights: Activity and Selectivity Tuning on Non-oxide Surfaces 136
6.4.1 Active Phase and In Situ Reconstruction 136
6.4.2 Activity Descriptors 136
6.4.3 Selectivity: Glycerol Oxidation vs. OER and Within the Glycerol Network 139
6.4.4 Consolidated Design Rules 140
6.5 Durability, Poisoning, and Hybrid Electrolyzer Architectures 140
6.5.1 Degradation Modes 141
6.5.2 Strategies for Durability and Poisoning Resistance 142
6.5.3 Alkaline-Alkaline and Hybrid Alkali-Acid Architectures 143
6.5.4 Device-level Benchmarking 143
6.6 Operando Characterization and Future Directions 144
6.6.1 Role of Operando and In Situ Methods 144
6.6.2 Key Techniques 144
6.6.3 From Operando Data to Design Rules 146
6.6.4 Future Directions 146
References 147
Part III Hydrazine-assisted Water Electrolysis 151
7 Metal Sulfides as Electrocatalysts for Hydrazine-assisted Water Electrolysis 153
Aravindhan Selvaraj, Hemalatha Parangusan, Dhanasekaran Vikraman, Hyun-Seok Kim, Akram Alfantazi, and K. Karuppasamy
7.1 Introduction 153
7.2
A Basic Understanding of N 2 H 4 -assisted HER 154
7.2.1 Parameters Required to Estimate the Catalytic Performance 154
7.2.2 Exchange Current Density (j 0) and Tafel Slope 155
7.2.3 Turnover Frequency 155
7.2.4 Stability 156
7.3 Hydrazine-assisted HER Applications 156
7.3.1 Nickel-based Catalysts 156
7.3.2 Cobalt-based Catalysts 158
7.4 Design and Mechanism 160
7.5 Conclusion 161
References 161
8 Metal Phosphides Electrocatalysts for Hydrazine-assisted Water Electrolysis 167
Rahul D. Kerkar
8.1 Introduction 167
8.2 Fundamentals of Hydrazine-assisted Water Electrolysis 170
8.3 Transition-metal Phosphides 171
8.3.1 Structure, Electronic Properties, and Relevance to Electrocatalysis 171
8.3.1.1 Crystal Structure and Classification of Metal Phosphides 171
8.3.1.2 Electronic Structure and Conductivity 172
8.3.1.3 Relevance to Electrocatalysis 173
8.3.2 Synthesis Strategies for Metal Phosphides 174
8.3.2.1 Phosphidation of Metal Hydroxide or Metal Oxide Precursors 174
8.3.2.2 Direct Solid-state Reaction 175
8.3.2.3 Hydrothermal Phosphidation 176
8.3.2.4 CO 2 Laser-assisted Method 176
8.3.2.5 Template or MOF-derived Methods 176
8.3.2.6 Electrochemical In Situ Phosphidation 177
8.4 Characterization Techniques 177
8.4.1 X-ray Diffraction 178
8.4.2 Transmission Electron Microscopy 179
8.4.3 X-ray Photoelectron Spectroscopy 179
8.4.4 Inductively Coupled Plasma 180
8.4.5 Study of Surface Area, Porosity, and Active Sites 180
8.5 Electrochemical Performance Evaluation 181
8.6 Post-characterization Techniques 183
8.7 Conclusion 184
References 185
9 Metal Carbides and Nitrides Electrocatalysts for Hydrazine-assisted Water Electrolysis 191
Binaya Kumar Sahu and Pooja Sahoo
9.1 Introduction 191
9.2 Structure and Properties of Metal Carbides and Nitrides 194
9.3 Fundamentals of Hydrazine-assisted Water Catalysis for Hydrogen Production 198
9.4 Fundamentals of Hydrazine-assisted Water Catalysis for Fuel Cells 200
9.5 Measurement Criteria for HzOR-assisted Water Electrocatalysis 202
9.5.1 Overpotential 202
9.5.2 Tafel Slope 202
9.5.3 Electrochemical Active Surface Area 203
9.5.4 Electrochemical Impedance 203
9.5.5 Stability 203
9.6 Metal Carbides for Hydrazine-assisted Water Electrocatalysis 204
9.7 Metal Nitrides for Hydrazine-assisted Water Electrocatalysis 209
9.8 Conclusion 212
Acknowledgments 213
References 213
10 Metal Alloy Electrocatalysts for Hydrazine-assisted Water Electrolysis 221
Shreyanka Shankar Naik
References 227
11 Metal Borides and Selenides for Hydrazine-assisted Water Electrolysis 231
Soumya Ranjan Mishra, Shalu Rawat, Vishwajit Chavda, and B. M. Nagaraja
11.1 Introduction 231
11.2 Fundamentals of Hz-WE 232
11.3 Chemistry and Structure of Metal Borides 234
11.3.1 Structural Features and Stability 234
11.3.2 Synthesis of Compositional Control 235
11.3.3 Electrocatalytic Behavior in Hz-WE 236
11.4 Chemistry and Structure of Metal Selenides 237
11.4.1 Structural Features and Stability 237
11.4.2 Synthesis and Compositional Control 237
11.4.3 Electrocatalytic Behavior in Hz-WE 238
11.5 Challenges and Future Prospects 241
11.6 Conclusion 242
Acknowledgments 242
References 243
12 Single-atom Electrocatalysts for Hydrazine-assisted Water Electrolysis 249
Talshyn Begildayeva and Juan A. Lopez-Ruiz
12.1 Introduction 249
12.2 SACs: What They Are, How They Work, and Why They Matter 251
12.3 HzOR as a Promising Alternative to the OER in Hybrid WE 256
12.4 Challenges for WE Coupled With Hydrazine Oxidation on SACs 261
References 262
Part IV Urea and Furfural-assisted Water Electrolysis 269
13 Metal Sulfides and Phosphides Electrocatalysts for Urea-assisted Water Electrolysis 271
Marciélli Karoline Rodrigues de Souza, Eduardo dos Santos Freitas Cardoso, and Marcos Roberto de Vasconcelos Lanza
13.1 Introduction 271
13.2 The Mechanism Involving UOR in Alkaline Media 272
13.3 Synthesis of Sulfides and Phosphides-based Electrocatalysts 274
13.3.1 Integrated Techniques for the Synthesis of Sulfides and Phosphides-based Electrocatalysts 274
13.3.1.1 Hydrothermal, Solvothermal, and Electrochemical Synthesis Techniques 274
13.4 Structural and Catalytic Performances of Metal Sulfides and Phosphides 275
13.4.1 Morphological and Interface Engineering 276
13.4.1.1 Heterostructures Engineering 276
13.4.1.2 Incorporation of Conductivity Phases and Controlled Morphology 279
13.4.2 Compositional Modulation and Synergistic Effects 280
13.4.2.1 Bimetallic Integration and Controlled Doping 280
13.4.3 Hybrid Architectures and MOF-derived Platforms 282
13.4.4 Summary of Structure-Performance Relationship 285
13.5 Conclusions 288
References 288
14 Metal Carbides and Nitrides Electrocatalysts for Urea and Furfural-assisted Water Electrolysis 293
Soorya S. Raj, M. L. Aruna Kumari, P. Keerthana
14.1 Introduction 293
14.2 Fundamentals of Urea and Furfural-assisted Water Electrolysis 294
14.2.1 Thermodynamics and Kinetics of UOR 294
14.2.2 FOR: Pathways and Value-added Products 295
14.2.3 Comparison with OER: Potential Reduction and Efficiency Gains 296
14.2.4 Dual Benefits: Sustainable Hydrogen Generation + Chemical Coproduction 296
14.3 MCNs as Electrocatalysts 297
14.3.1 Unique Physicochemical Properties 297
14.3.2 Synergy with Transition Metals for Enhanced Activity 297
14.3.3 Stability and Corrosion Resistance in Harsh Electrolytes 298
14.3.4 Structure-Activity Relationship Principles 298
14.4Synthesis and Strategies 299
14.4.1 Carbothermal Reduction and Nitridation Methods 299
14.4.2 Template-assisted Synthesis 300
14.4.3 Sol-Gel and Hydrothermal Approaches 300
14.4.4 Plasma-enhanced and CVD Techniques 300
14.4.5 Challenges in Phase Control, Morphology, and Scalability 300
14.5 MCNs for UOR 302
14.5.1 Molybdenum and Tungsten Carbides/Nitrides 302
14.5.2 Iron, Cobalt, and Nickel Carbides/Nitrides 302
14.5.3 Mixed-metal Carbides and Nitrides 303
14.5.4 Reaction Mechanism Insights and Performance Benchmarks 303
14.6 MCNs for FOR 303
14.6.1 Ni-, Mo-, and Co-based Carbides/Nitrides for Furfural Valorization 304
14.6.2 Selectivity Control and Product Distribution 304
14.6.3 Coupling Furfural Oxidation with HER 305
14.7 Challenges and Future Perspectives 306
14.8 Conclusion 306
References 307
15 Metal Sulfides and Phosphides Electrocatalysts for Furfural-assisted Water Electrolysis 313
Jessica J. P. Nascimento, Paulo N. S. Casciano, Francisco W. P. Ribeiro, Thiago M. B. F. Oliveira, Adriana N. Correia, and Pedro de Lima-Neto
15.1 Introduction 313
15.2 Importance of Transition-metal-based Catalysts 315
15.3 Electrocatalytic Performance for FF Compounds Oxidation and Her 317
15.3.1 Metal Phosphides Electrocatalysts for FF-assisted Water Electrolysis 319
15.3.2 Metal Sulfides Electrocatalysts for FF-assisted Water Electrolysis 321
15.4 Pathways of FF Oxidation Reaction 324
15.4.1 Pathways in Acidic Media 324
15.4.2 Pathways in Alkaline/Neutral Media 324
15.4.3 Electrochemical Synergy Between FOR and HER 326
15.5 Challenges and Prospects 327
Acknowledgments 327
References 327
16 Single-atom Electrocatalysts for Urea and Furfural-assisted Water Electrolysis 337
Xiangyu You, Julio C. Lourenço, Tulio P. Porto, Dhananjai Pangotra, Luciana Vieira, Huize Wang, Marc Ledendecker, Robson S. Rocha, Alexsandro J. dos Santos, Marcos Roberto de Vasconcelos Lanza, Gilberto Maia, and Guilherme V. Fortunato
16.1 Introduction 338
16.2 Fundamentals of Single-atom Electrocatalysts 338
16.2.1 Definition and Features of SACs 338
16.2.2 Common Synthesis Methods 340
16.2.3 Characterization Techniques 341
16.3 Advantages of Using SACs for Electrooxidation Reactions and the Stability Issues 342
16.4 UOR and SACs 343
16.4.1 Mechanisms of UOR, Kinetics, and Energy Advantages Compared to OER 343
16.4.2 State-of-the-art Electrocatalysts and the Advantages of SACs for Uor 345
16.4.3 Long-term Stability and Practical Perspectives of SACs for UOR 346
16.5 Furfural Oxidation and SACs 347
16.5.1 Oxidation Pathways and Products of Furfural 347
16.5.2 Electrocatalysts for FOR and Opportunities for SACs 349
16.6 Hybrid Electrolyzer Configuration, Integration, and Challenges of Using SACs 350
16.6.1 System-level Considerations 350
16.6.2 Catalyst-level Considerations and SAC Challenges 351
16.6.3 Selectivity-Current Density Trade-offs 353
16.7 Conclusion 353
References 354
17 Non-oxide Electrocatalysts for Glucose-oxidation-coupled Water Electrolysis 365
P. H. Gangadharagowda, K. Chandana, S. K. Vinoth, K. Yogesh Kumar , and Arun Varghese
17.1 Introduction 365
17.2 Importance of Glucose-oxidation-coupled Water Electrolysis 367
17.3 Performance Evaluation Using Non-oxide Electrocatalysts 370
17.4 Conclusions and Future Perspectives 380
References 380
Part V Future Prospects 385
18 Future Prospects and Commercialization of Energy-saving Hybrid Water Electrolysis 387
Juan A. Lopez-Ruiz and Talshyn Begildayeva
18.1 Introduction 387
18.2 Bridging the Lab-to-plant Divide in Electrolyzers 388
18.3 Key Performance Indicators 393
18.3.1 Normalized Reaction Rates 394
18.3.2 Energy Consumption and Efficiency 396
18.4 Process Consideration 397
18.4.1 Integration of Oxidation and Reduction Processes into a Single Unit 398
18.4.2 Mild Operation Conditions 401
18.4.3 Simpler and Safer Operation 401
18.4.4 Electrification With Diverse Sources 402
18.5 Scale-up Considerations 402
18.5.1 Electrolyzer Design 403
18.5.2 Component Manufacturing 404
18.5.3 Dynamic Operations and Advanced Controls 405
18.6 Future Research Direction and Commercialization Strategies 406
References 409
Index 415
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