Explore the potential of electrocatalysis to balance an off-kilter natural carbon cycle
In Electrocatalysis in Balancing the Natural Carbon Cycle, accomplished researcher and author, Yaobing Wang, delivers a focused examination of why and how to solve the unbalance of the natural carbon cycle with electrocatalysis. The book introduces the natural carbon cycle and analyzes current bottlenecks being caused by human activities. It then examines fundamental topics, including CO2 reduction, water splitting, and small molecule (alcohols and acid) oxidation to prove the feasibility and advantages of using electrocatalysis to tune the unbalanced carbon cycle.
You’ll realize modern aspects of electrocatalysis through the operando diagnostic and predictable mechanistic investigations. Further, you will be able to evaluate and manage the efficiency of the electrocatalytic reactions. The distinguished author presents a holistic view of solving an unbalanced natural carbon cycle with electrocatalysis.
Readers will also benefit from the inclusion of:- A thorough introduction to the natural carbon cycle and the anthropogenic carbon cycle, including inorganic carbon to organic carbon and vice versa - An exploration of electrochemical catalysis processes, including water splitting and the electrochemistry CO2 reduction reaction (ECO2RR) - A practical discussion of water and fuel basic redox parameters, including electrocatalytic materials and their performance evaluation in different electrocatalytic cells - A perspective of the operando approaches and computational fundamentals and advances of different electrocatalytic redox reactions
Perfect for electrochemists, catalytic chemists, environmental and physical chemists, and inorganic chemists, Electrocatalysis in Balancing the Natural Carbon Cycle will also earn a place in the libraries of solid state and theoretical chemists seeking a one-stop reference for all aspects of electrocatalysis in carbon cycle-related reactions.
Table of Contents
Preface xv
Acknowledgments xix
Part I Introduction 1
1 Introduction 3
References 5
Part II Natural Carbon Cycle 7
2 Natural Carbon Cycle and Anthropogenic Carbon Cycle 9
2.1 Definition and General Process 9
2.2 From Inorganic Carbon to Organic Carbon 10
2.3 From Organic Carbon to Inorganic Carbon 11
2.4 Anthropogenic Carbon Cycle 11
2.4.1 Anthropogenic Carbon Emissions 12
2.4.2 Capture and Recycle of CO2 from the Atmosphere 13
2.4.3 Fixation and Conversion of CO2 14
2.4.3.1 Photochemical Reduction 14
2.4.3.2 Electrochemical Reduction 15
2.4.3.3 Chemical/Thermo Reforming 16
2.4.3.4 Physical Fixation 16
2.4.3.5 Anthropogenic Carbon Conversion and Emissions Via
Electrochemistry 17
References 18
Part III Electrochemical Catalysis Process 21
3 Electrochemical Catalysis Processes 23
3.1 Water Splitting 23
3.1.1 Reaction Mechanism 23
3.1.1.1 Mechanism of OER 23
3.1.1.2 Mechanism of ORR 24
3.1.1.3 Mechanism of HER 26
3.1.2 General Parameters to Evaluate Water Splitting 27
3.1.2.1 Tafel Slope 27
3.1.2.2 TOF 27
3.1.2.3 Onset/Overpotential 28
3.1.2.4 Stability 28
3.1.2.5 Electrolyte 28
3.2 Electrochemistry CO2 Reduction Reaction (ECDRR) 29
3.2.1 Possible Reaction Pathways of ECDRR 29
3.2.1.1 Formation of HCOO- or HCOOH 29
3.2.1.2 Formation of CO 30
3.2.1.3 Formation of C1 Products 30
3.2.1.4 Formation of C2 Products 31
3.2.1.5 Formation of CH3COOH and CH3COO- 33
3.2.1.6 Formation of n-Propanol (C3 Product) 33
3.2.2 General Parameters to Evaluate ECDRR 34
3.2.2.1 Onset Potential 34
3.2.2.2 Faradaic Efficiency 34
3.2.2.3 Partial Current Density 34
3.2.2.4 Environmental Impact and Cost 35
3.2.2.5 Electrolytes 35
3.2.2.6 Electrochemical Cells 36
3.3 Small Organic Molecules Oxidation 36
3.3.1 The Mechanism of Electrochemistry HCOOH Oxidation 36
3.3.2 The Mechanism of Electro-oxidation of Alcohol 37
References 40
Part IV Water Splitting and Devices 43
4 Water Splitting Basic Parameter/Others 45
4.1 Composition and Exact Reactions in Different pH Solution 45
4.2 Evaluation of the Catalytic Activity 47
4.2.1 Overpotential 47
4.2.2 Tafel Slope 48
4.2.3 Stability 49
4.2.4 Faradaic Efficiency 49
4.2.5 Turnover Frequency 50
References 50
5 H2O Oxidation 53
5.1 Regular H2O Oxidation 53
5.1.1 Noble Metal Catalysts 53
5.1.2 Other Transition Metals 64
5.1.3 Other Catalysts 72
5.2 Photo-Assisted H2O Oxidation 76
5.2.1 Metal Compound-Based Catalysts 76
5.2.2 Metal-Metal Heterostructure Catalysts 80
5.2.3 Metal-Nonmetal Heterostructure Catalysts 86
References 88
6 H2O Reduction and Water Splitting Electrocatalytic Cell 91
6.1 Noble-Metal-Based HER Catalysts 91
6.2 Non-Noble Metal Catalysts 93
6.3 Water Splitting Electrocatalytic Cell 96
References 99
Part V H2 Oxidation/O2 Reduction and Device 101
7 Introduction 103
7.1 Electrocatalytic Reaction Parameters 104
7.1.1 Electrochemically Active Surface Area (ECSA) 104
7.1.1.1 Test Methods 104
7.1.2 Determination Based on the Surface Redox Reaction 104
7.1.3 Determination by Electric Double-Layer Capacitance Method 105
7.1.4 Kinetic and Exchange Current Density (jk and j0) 105
7.1.4.1 Definition 105
7.1.4.2 Calculation 106
7.1.5 Overpotential HUPD 106
7.1.6 Tafel Slope 108
7.1.7 Halfwave Potentials 108
References 108
8 Hydrogen Oxidation Reaction (HOR) 111
8.1 Mechanism for HOR 111
8.1.1 Hydrogen Bonding Energy (HBE) 111
8.1.2 Underpotential Deposition (UPD) of Hydrogen 112
8.2 Catalysts for HOR 112
8.2.1 Pt-based Materials 112
8.2.2 Pd-Based Materials 120
8.2.3 Ir-Based Materials 121
8.2.4 Rh-Based Materials 121
8.2.5 Ru-Based Materials 121
8.2.6 Non-noble Metal Materials 122
References 130
9 Oxygen Reduction Reaction (ORR) 133
9.1 Mechanism for ORR 133
9.1.1 Battery System and Damaged Electrodes 133
9.1.2 Intermediate Species 134
9.2 Catalysts in ORR 134
9.2.1 Noble Metal Materials 134
9.2.1.1 Platinum/Carbon Catalyst 138
9.2.1.2 Pd and Pt 145
9.2.2 Transition Metal Catalysts 145
9.2.3 Metal-Free Catalysts 149
9.3 Hydrogen Peroxide Synthesis 154
9.3.1 Catalysts Advances 154
9.3.1.1 Pure Metals 154
9.3.1.2 Metal Alloys 156
9.3.1.3 Carbon Materials 157
9.3.1.4 Electrodes and Reaction Cells 158
References 161
10 Fuel Cell and Metal-Air Battery 167
10.1 H2 Fuel Cell 167
10.2 Metal-Air Battery 170
10.2.1 Metal-Air Battery Structure 171
References 181
Part VI Small Organic Molecules Oxidation and Device 183
11 Introduction 185
11.1 Primary Measurement Methods and Parameters 186
11.1.1 Primary Measurement Methods 186
11.1.2 Primary Parameter 193
References 197
12 C1 Molecule Oxidation 199
12.1 Methane Oxidation 199
12.1.1 Reaction Mechanism 199
12.1.1.1 Solid-Liquid-Gas Reaction System 199
12.1.2 Acidic Media 199
12.1.3 Alkaline or Neutral Media 201
12.2 Methanol Oxidation 203
12.2.1 Reaction Thermodynamics and Mechanism 203
12.2.2 Catalyst Advances 204
12.2.2.1 Pd-Based Catalysts 204
12.2.2.2 Pt-Based Catalysts 208
12.2.2.3 Platinum-Based Nanowires 208
12.2.2.4 Platinum-Based Nanotubes 210
12.2.2.5 Platinum-Based Nanoflowers 212
12.2.2.6 Platinum-Based Nanorods 214
12.2.2.7 Platinum-Based Nanocubes 215
12.2.3 Pt-Ru System 217
12.2.4 Pt-Sn Catalysts 218
12.3 Formic Acid Oxidation 219
12.3.1 Reaction Mechanism 219
12.3.2 Catalyst Advances 220
12.3.2.1 Pd-Based Catalysts 220
12.3.2.2 Pt-Based Catalysts 223
References 226
13 C2+ Molecule Oxidation 235
13.1 Ethanol Oxidation 235
13.1.1 Reaction Mechanism 235
13.1.2 Catalyst Advances 235
13.1.2.1 Pd-Based Catalysts 235
13.1.2.2 Pt-Based Catalysts 239
13.1.2.3 Pt-Sn System 243
13.2 Glucose Oxidase 250
13.3 Ethylene Glycol Oxidation 251
13.4 Glycerol Oxidation 251
References 254
14 Fuel Cell Devices 257
14.1 Introduction 257
14.2 Types of Direct Liquid Fuel Cells 258
14.2.1 Acid and Alkaline Fuel Cells 258
14.2.2 Direct Methanol Fuel Cells (DMFCs) 260
14.2.3 Direct Ethanol Fuel Cells (DEFCs) 261
14.2.4 Direct Ethylene Glycol Fuel Cells (DEGFCs) 261
14.2.5 Direct Glycerol Fuel Cells (DGFCs) 262
14.2.6 Direct Formic Acid Fuel Cells (DFAFCs) 262
14.2.7 Direct Dimethyl Ether Fuel Cells (DDEFCs) 263
14.2.8 Other DLFCs 263
14.2.9 Challenges of DLFCs 264
14.2.10 Fuel Conversion and Cathode Flooding 264
14.2.11 Chemical Safety and By-product Production 265
14.2.12 Unproven Long-term Durability 265
References 267
Part VII CO2 Reduction and Device 271
15 Introduction 273
15.1 Basic Parameters of the CO2 Reduction Reaction 276
15.1.1 The Fundamental Parameters to Evaluate the Catalytic Activity 276
15.1.1.1 Overpotential (𝜂) 276
15.1.1.2 Faradaic Efficiency (FE) 276
15.1.1.3 Current Density ( j) 277
15.1.1.4 Energy Efficiency (EE) 277
15.1.1.5 Tafel Slope 278
15.1.2 Factors Affecting ECDRR 278
15.1.2.1 Solvent/Electrolyte 278
15.1.2.2 pH 280
15.1.2.3 Cations and Anions 281
15.1.2.4 Concentration 282
15.1.2.5 Temperature and Pressure Effect 282
15.1.3 Electrode 283
15.1.3.1 Loading Method 283
15.1.3.2 Preparation 284
15.1.3.3 Experimental Process and Analysis Methods 284
References 285
16 Electrocatalysts-1 289
16.1 Heterogeneous Electrochemical CO2 Reduction Reaction 289
16.2 Thermodynamic and Kinetic Parameters of Heterogeneous CO2 Reduction in Liquid Phase 289
16.2.1 Bulk Metals 293
16.2.2 Nanoscale Metal and Oxidant Metal Catalysts 294
16.2.2.1 Gold (Au) 295
16.2.2.2 Silver (Ag) 296
16.2.2.3 Palladium (Pd) 297
16.2.2.4 Zinc (Zn) 298
16.2.2.5 Copper (Cu) 299
16.2.3 Bimetallic/Alloy 301
References 306
17 Electrocatalysts-2 309
17.1 Single-Atom Metal-Doped Carbon Catalysts (SACs) 309
17.1.1 Nickel (Ni)-SACs 309
17.1.2 Cobalt (Co)-SACs 311
17.1.3 Iron (Fe)-SACs 311
17.1.4 Zinc (Zn)-SACs 314
17.1.5 Copper (Cu)-SACs 314
17.1.6 Other 316
17.2 Metal Nanoparticles-Doped Carbon Catalysts 317
17.3 Porous Organic Material 320
17.3.1 Metal Organic Frameworks (MOFs) 320
17.3.2 Covalent Organic Frameworks (COFs) 321
17.3.3 Metal-Free Catalyst 322
17.4 Metal-Free Carbon-Based Catalyst 322
17.4.1 Other Metal-Free Catalyst 324
17.5 Electrochemical CO Reduction Reaction 324
17.5.1 The Importance of CO Reduction Study 324
17.5.2 Advances in CO Reduction 326
References 327
18 Devices 331
18.1 H-Cell 331
18.2 Flow Cell 333
18.3 Requirements and Challenges for Next-Generation CO2 Reduction Cell 338
18.3.1 Wide Range of Electrocatalysts 338
18.3.2 Fundamental Factor Influencing the Catalytic Activity for ECDRR 339
18.3.3 Device Engineering 340
References 342
Part VIII Computations-Guided Electrocatalysis 345
19 Insights into the Catalytic Process 347
19.1 Electric Double Layer 347
19.2 Kinetics and Thermodynamics 349
19.3 Electrode Potential Effects 350
References 352
20 Computational Electrocatalysis 355
20.1 Computational Screening Toward Calculation Theories 356
20.2 Reactivity Descriptors 358
20.2.1 d-band Theory Motivates Electronic Descriptor 359
20.2.2 Coordination Numbers Motives Structure Descriptor 361
20.3 Scaling Relationships: Applications of Descriptors 361
20.4 The Activity Principles and the Volcano Curve 363
20.5 DFT Modeling 366
20.5.1 CHE Model 367
20.5.2 Solvation Models 368
20.5.3 Kinetic Modeling 371
References 374
21 Theory-Guided Rational Design 377
21.1 Descriptors-Guided Screening 377
21.2 Scaling Relationship-Guided Trends 380
21.2.1 Reactivity Trends of ECR 380
21.2.2 Reactivity Trends of O-included Reactions 382
21.2.3 Reactivity Trends of H-included Reactions 385
21.3 DOS-Guided Models and Active Sites 386
References 388
22 DFT Applications in Selected Electrocatalytic Systems 391
22.1 Unveiling the Electrocatalytic Mechanism 391
22.1.1 ECR Reaction 393
22.1.2 OER Reaction 394
22.1.3 ORR Reaction 396
22.1.4 HER Reaction 397
22.1.5 HOR Reaction 398
22.1.6 CO Oxidation Reaction 400
22.1.7 FAOR Reaction 402
22.1.8 MOR Reaction 402
22.1.9 EOR Reaction 404
22.2 Understanding the Electrocatalytic Environment 406
22.2.1 Solvation Effects 406
22.2.2 pH Effects 409
22.3 Analyzing the Electrochemical Kinetics 410
22.4 Perspectives, Challenges, and Future Direction of DFT Computation in Electrocatalysis 413
References 414
Part IX Potential of In Situ Characterizations for Electrocatalysis 421
References 422
23 In Situ Characterization Techniques 423
23.1 Optical Characterization Techniques 423
23.1.1 Infrared Spectroscopy 423
23.1.2 Raman Spectroscopy 424
23.1.3 UV-vis Spectroscopy 426
23.2 X-Ray Characterization Techniques 427
23.2.1 X-Ray Diffraction (XRD) 429
23.2.2 X-Ray Absorption Spectroscopy (XAS) 429
23.2.3 X-Ray Photoelectron Spectroscopy (XPS) 431
23.3 Mass Spectrometric Characterization Techniques 431
23.4 Electron-Based Characterization Techniques 432
23.4.1 Transmission Electron Microscopy (TEM) 434
23.4.2 Scanning Probe Microscopy (SPM) 434
References 436
24 In Situ Characterizations in Electrocatalytic Cycle 441
24.1 Investigating the Real Active Centers 441
24.1.1 Monitoring the Electronic Structure 442
24.1.2 Monitoring the Atomic Structure 444
24.1.3 Monitoring the Catalyst Phase Transformation 446
24.2 Investigating the Reaction Mechanism 449
24.2.1 Through Adsorption/Activation Understanding 450
24.2.2 Through Intermediates In Situ Probing 451
24.2.3 Through Catalytic Product In Situ Detections 454
24.3 Evaluating the Catalyst Stability/Decay 457
24.4 Revealing the Interfacial-Related Insights 460
24.5 Conclusion 462
References 462
Part X Electrochemical Catalytic Carbon Cycle 465
References 466
25 Electrochemical CO2 Reduction to Fuels 467
References 479
26 Electrochemical Fuel Oxidation 483
References 495
27 Evaluation and Management of ECC 499
27.1 Basic Performance Index 499
27.2 CO2 Capture and Fuel Transport 500
27.3 External Management 500
27.4 General Outlook 502
References 505
Index 507
