Electrocatalysis in Balancing the Natural Carbon Cycle

Preface Acknowledgments Part I Introduction 1 Introduction Reference Part II Natural Carbon Cycle 2 Natural Carbon Cycle and Anthropogenic Carbon Cycle 2.1 Definition and General Process 2.2 From Inorganic Carbon to Organic Carbon 2.3 From Organic Carbon to Inorganic Carbon 2.4 Anthropogenic Carbon Cycle 2.4.1 Anthropogenic Carbon Emissions 2.4.2 Capture and Recycle of CO2 from the Atmosphere 2.4.3 Fixation and Conversion of CO2 2.4.3.1 Photochemical Reduction 2.4.3.2 Electrochemical Reduction 2.4.3.3 Chemical/Thermo Reforming 2.4.3.4 Physical Fixation 2.4.3.5 Anthropogenic Carbon Conversion and Emissions Via Electrochemistry References Part III Electrochemical Catalysis Process 3 Electrochemical Catalysis Processes 3.1 Water Splitting 3.1.1 Reaction Mechanism 3.1.1.1 Mechanism of OER 3.1.1.2 Mechanism of ORR 3.1.1.3 Mechanism of HER 3.1.2 General Parameters to Evaluate Water Splitting 3.1.2.1 Tafel Slope 3.1.2.2 TOF 3.1.2.3 Onset/Overpotential 3.1.2.4 Stability 3.1.2.5 Electrolyte 3.2 Electrochemistry CO2 Reduction Reaction (ECDRR) 3.2.1 Possible Reaction Pathways of ECDRR 3.2.1.1 Formation of HCOO- or HCOOH 3.2.1.2 Formation of CO 3.2.1.3 Formation of C1 Products 3.2.1.4 Formation of C2 Products 3.2.1.5 Formation of CH3COOH and CH3COO- 3.2.1.6 Formation of n-Propanol (C3 Product) 3.2.2 General Parameters to Evaluate ECDRR 3.2.2.1 Onset Potential 3.2.2.2 Faradaic Efficiency 3.2.2.3 Partial Current Density 3.2.2.4 Environmental Impact and Cost 3.2.2.5 Electrolytes 3.2.2.6 Electrochemical Cells 3.3 Small Organic Molecules Oxidation 3.3.1 The Mechanism of Electrochemistry HCOOH Oxidation 3.3.2 The Mechanism of Electro-oxidation of Alcohol References Part IV Water Splitting and Devices 4 Water Splitting Basic Parameter/Others 4.1 Composition and Exact Reactions in Different pH Solution 4.2 Evaluation of the Catalytic Activity 4.2.1 Overpotential 4.2.2 Tafel Slope 4.2.3 Stability 4.2.4 Faradaic Efficiency 4.2.5 Turnover Frequency References 5 H2O Oxidation 5.1 Regular H2O Oxidation 5.1.1 Noble Metal Catalysts 5.1.2 Other Transition Metals 5.1.3 Other Catalysts 5.2 Photo-Assisted H2O Oxidation 5.2.1 Metal Compound-Based Catalysts 5.2.2 Metal-Metal Heterostructure Catalysts 5.2.3 Metal-Nonmetal Heterostructure Catalysts References 6 H2O Reduction and Water Splitting Electrocatalytic Cell 6.1 Noble-Metal-Based HER Catalysts 6.2 Non-Noble Metal Catalysts 6.3 Water Splitting Electrocatalytic Cell References Part V H2 Oxidation/O2 Reduction and Device 7 Introduction 7.1 Electrocatalytic Reaction Parameters 7.1.1 Electrochemically Active Surface Area (ECSA) 7.1.1.1 Test Methods 7.1.2 Determination Based on the Surface Redox Reaction 7.1.3 Determination by Electric Double-Layer Capacitance Method 7.1.4 Kinetic and Exchange Current Density (jk and j0) 7.1.4.1 Definition 7.1.4.2 Calculation 7.1.5 Overpotential HUPD 7.1.6 Tafel Slope 7.1.7 Halfwave Potentials References 8 Hydrogen Oxidation Reaction (HOR) 8.1 Mechanism for HOR 8.1.1 Hydrogen Bonding Energy (HBE) 8.1.2 Underpotential Deposition (UPD) of Hydrogen 8.2 Catalysts for HOR 8.2.1 Pt-based Materials 8.2.2 Pd-Based Materials 8.2.3 Ir-Based Materials 8.2.4 Rh-Based Materials 8.2.5 Ru-Based Materials 8.2.6 Non-noble Metal Materials References 9 Oxygen Reduction Reaction (ORR) 9.1 Mechanism for ORR 9.1.1 Battery System and Damaged Electrodes 9.1.2 Intermediate Species 9.2 Catalysts in ORR 9.2.1 Noble Metal Materials 9.2.1.1 Platinum/Carbon Catalyst 9.2.1.2 Pd and Pt 9.2.2 Transition Metal Catalysts 9.2.3 Metal-Free Catalysts 9.3 Hydrogen Peroxide Synthesis 9.3.1 Catalysts Advances 9.3.1.1 Pure Metals 9.3.1.2 Metal Alloys 9.3.1.3 Carbon Materials 9.3.1.4 Electrodes and Reaction Cells References 10 Fuel Cell and Metal-Air Battery 10.1 H2 Fuel Cell 10.2 Metal-Air Battery 10.2.1 Metal-Air Battery Structure References Part VI Small Organic Molecules Oxidation and Device 11 Introduction 11.1 Primary Measurement Methods and Parameters 11.1.1 Primary Measurement Methods 11.1.2 Primary Parameter References 12 C1 Molecule Oxidation 12.1 Methane Oxidation 12.1.1 Reaction Mechanism 12.1.1.1 Solid-Liquid-Gas Reaction System 12.1.2 Acidic Media 12.1.3 Alkaline or Neutral Media 12.2 Methanol Oxidation 12.2.1 Reaction Thermodynamics and Mechanism 12.2.2 Catalyst Advances 12.2.2.1 Pd-Based Catalysts 12.2.2.2 Pt-Based Catalysts 12.2.2.3 Platinum-Based Nanowires 12.2.2.4 Platinum-Based Nanotubes 12.2.2.5 Platinum-Based Nanoflowers 12.2.2.6 Platinum-Based Nanorods 12.2.2.7 Platinum-Based Nanocubes 12.2.3 Pt-Ru System 12.2.4 Pt-Sn Catalysts 12.3 Formic Acid Oxidation 12.3.1 Reaction Mechanism 12.3.2 Catalyst Advances 12.3.2.1 Pd-Based Catalysts 12.3.2.2 Pt-Based Catalysts References 13 C2+ Molecule Oxidation 13.1 Ethanol Oxidation 13.1.1 Reaction Mechanism 3.1.2 Catalyst Advances 13.1.2.1 Pd-Based Catalysts 13.1.2.2 Pt-Based Catalysts 13.1.2.3 Pt-Sn System 13.2 Glucose Oxidase 13.3 Ethylene Glycol Oxidation 13.4 Glycerol Oxidation References 14 Fuel Cell Devices 14.1 Introduction 14.2 Types of Direct Liquid Fuel Cells 14.2.1 Acid and Alkaline Fuel Cells 14.2.2 Direct Methanol Fuel Cells (DMFCs) 14.2.3 Direct Ethanol Fuel Cells (DEFCs) 14.2.4 Direct Ethylene Glycol Fuel Cells (DEGFCs) 14.2.5 Direct Glycerol Fuel Cells (DGFCs) 14.2.6 Direct Formic Acid Fuel Cells (DFAFCs) 14.2.7 Direct Dimethyl Ether Fuel Cells (DDEFCs) 14.2.8 Other DLFCs 14.2.9 Challenges of DLFCs 14.2.10 Fuel Conversion and Cathode Flooding 14.2.11 Chemical Safety and By-product Production 14.2.12 Unproven Long-term Durability References Part VII CO2 Reduction and Device 15 Introduction 15.1 Basic Parameters of the CO2 Reduction Reaction 15.1.1 The Fundamental Parameters to Evaluate the Catalytic Activity 15.1.1.1 Overpotential 15.1.1.2 Faradaic Efficiency (FE) 15.1.1.3 Current Density 15.1.1.4 Energy Efficiency (EE) 15.1.1.5 Tafel Slope 15.1.2 Factors Affecting ECDRR 15.1.2.1 Solvent/Electrolyte 15.1.2.2 pH 15.1.2.3 Cations and Anions 15.1.2.4 Concentration 15.1.2.5 Temperature and Pressure Effect 15.1.3 Electrode 15.1.3.1 Loading Method 15.1.3.2 Preparation 15.1.3.3 Experimental Process and Analysis Methods References 16 Electrocatalysts-1 16.1 Heterogeneous Electrochemical CO2 Reduction Reaction 16.2 Thermodynamic and Kinetic Parameters of Heterogeneous CO2 Reduction in Liquid Phase 16.2.1 Bulk Metals 16.2.2 Nanoscale Metal and Oxidant Metal Catalysts 16.2.2.1 Gold (Au) 16.2.2.2 Silver (Ag) 16.2.2.3 Palladium (Pd) 16.2.2.4 Zinc (Zn) 16.2.2.5 Copper (Cu) 16.2.3 Bimetallic/Alloy References 17 Electrocatalysis-2 17.1 Single-Atom Metal-Doped Carbon Catalysts (SACs) 17.1.1 Nickel (Ni)-SACs 17.1.2 Cobalt (Co)-SACs 17.1.3 Iron (Fe)-SACs 17.1.4 Zinc (Zn)-SACs 17.1.5 Copper (Cu)-SACs 17.1.6 Other 17.2 Metal Nanoparticles-Doped Carbon Catalysts 17.3 Porous Organic Material 17.3.1 Molecular Organic Frameworks (MOFs) 17.3.2 Covalent Organic Frameworks (COFs) 17.3.3 Metal-Free Catalyst 17.4 Metal-Free Carbon-Based Catalyst 17.4.1 Other Metal-Free Catalyst 17.5 Electrochemical CO Reduction Reaction 17.5.1 The Importance of CO Reduction Study 17.5.2 Advances in CO Reduction References 18 Devices 18.1 H-Cell 18.2 Flow Cell 18.3 Requirements and Challenges for Next-Generation CO2 Reduction Cell 18.3.1 Wide Range of Electrocatalysts 18.3.2 Fundamental Factor Influencing the Catalytic Activity for ECDRR 18.3.3 Device Engineering References Part VIII Computations-Guided Electrocatalysis 19 Insights into the Catalytic Process 19.1 Electric Double Layer 19.2 Kinetics and Thermodynamics 19.3 Electrode Potential Effects References 20 Computational Electrocatalysis 20.1 Computational Screening Toward Calculation Theories 20.2 Reactivity Descriptors 20.2.1 d-band Theory Motivates Electronic Descriptor 20.2.2 Coordination Numbers Motives Structure Descriptor 20.3 Scaling Relationships: Applications of Descriptors 20.4 The Activity Principles and the Volcano Curve 20.5 DFT Modeling 20.5.1 CHE Model 20.5.2 Solvation Models 20.5.3 Kinetic Modeling References 21 Theory-Guided Rational Design 21.1 Descriptors-Guided Screening 21.2 Scaling Relationship-Guided Trends 21.2.1 Reactivity Trends of ECR 21.2.2 Reactivity Trends of O-included Reactions 21.2.3 Reactivity Trends of H-included Reactions 21.3 DOS-Guided Models and Active Sites References 22 DFT Applications in Selected Electrocatalytic Systems 22.1 Unveiling the Electrocatalytic Mechanism 22.1.1 ECR Reaction 22.1.2 OER Reaction 22.1.3 ORR Reaction 22.1.4 HER Reaction 22.1.5 HOR Reaction 22.1.6 CO Oxidation Reaction 22.1.7 FAOR Reaction 22.1.8 MOR Reaction 22.1.9 EOR Reaction 22.2 Understanding the Electrocatalytic Environment 22.2.1 Solvation Effects 22.2.2 pH Effects 22.3 Analyzing the Electrochemical Kinetics 22.4 Perspectives, Challenges, and Future Direction of DFT Computation in Electrocatalysis References Part IX Potential of In Situ Characterizations for Electrocatalysis References 23 In Situ Characterization Techniques 23.1 Optical Characterization Techniques 23.1.1 Infrared Spectroscopy 23.1.2 Raman Spectroscopy 23.1.3 UV-vis Spectroscopy 23.2 X-Ray Characterization Techniques 23.2.1 X-Ray Diffraction (XRD) 23.2.2 X-Ray Absorption Spectroscopy (XAS) 23.2.3 X-Ray Photoelectron Spectroscopy (XPS) 23.3 Mass Spectrometric Characterization Techniques 23.4 Electron-Based Characterization Techniques 23.4.1 Transmission Electron Microscopy (TEM) 23.4.2 Scanning Probe Microscopy (SPM) References 24 In Situ Characterizations in Electrocatalytic Cycle 24.1 Investigating the Real Active Centers 24.1.1 Monitoring the Electronic Structure 24.1.2 Monitoring the Atomic Structure 24.1.3 Monitoring the Catalyst Phase Transformation 24.2 Investigating the Reaction Mechanism 24.2.1 Through Adsorption/Activation Understanding 24.2.2 Through Intermediates In Situ Probing 24.2.3 Through Catalytic Product In Situ Detections 24.3 Evaluating the Catalyst Stability/Decay 24.4 Revealing the Interfacial-Related Insights 24.5 Conclusion References Part X Electrochemical Catalytic Carbon Cycle References 25 Electrochemical CO2 Reduction to Fuels References 26 Electrochemical Fuel Oxidation References 27 Evaluation and Management of ECC 27.1 Basic Performance Index 27.2 CO2 Capture and Fuel Transport 27.3 External Management 27.4 General Outlook References