Applied Polyoxometalate-Based Electrocatalysis

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Applied Polyoxometalate-Based Electrocatalysis
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Contents
Part I. Fundamentals
	1. Introduction to Polyoxometalates
		1.1 Introduction
		1.2 Polyoxometalate Structures
			1.2.1 Synthetic Methodologies
			1.2.2 Lindqvist Structure
			1.2.3 Keggin Structure
			1.2.4 Wells–Dawson Structure
			1.2.5 Anderson–Evans Structure
			1.2.6 Preyssler Structure
			1.2.7 Other POM Structures
		1.3 POM‐based Composites and Materials
		1.4 Conclusions
		References
	2. Design and Strategies to Enhance the Electrochemical Properties of POM Nanomaterials for Electrocatalysis
		2.1 Introduction
			2.1.1 Structure Bonding and Formation
			2.1.2 POM Archetypes: Keggin and Wells–Dawson
			2.1.3 Factors Influencing the Catalytic Role of POMs
			2.1.4 The Structure–Redox Relationship in POMs
		2.2 Design Approaches via Organofunctionalization
			2.2.1 Transition‐metal‐substituted POMs (TMS‐POMs)
			2.2.2 Class I Hybrid POMs
			2.2.3 Class II Hybrid POMs
			2.2.4 Asymmetric Systems
			2.2.5 Supramolecular Assembly
			2.2.6 Immobilization Techniques
				2.2.6.1 Surface Immobilization
				2.2.6.2 Nanoencapsulation
		2.3 Conclusion
		References
Part II. Polyoxometalates for Oxidative Electrocatalysis
	3. POM‐based Electrocatalysts for l‐Cysteine and NADH Oxidation
		3.1 Introduction
		3.2 The Electrocatalytic Oxidation of l‐cysteine (Cys)
			3.2.1 V‐containing POMs as Electrocatalysts in Homogeneous Phase
			3.2.2 Ce‐containing POMs as Electrocatalysts in Homogeneous Phase
			3.2.3 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Carbon Paste Electrodes
			3.2.4 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Layer‐by‐layer modified Electrodes
			3.2.5 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Layer‐by‐layer and Nanoparticle‐modified Electrodes
		3.3 The Electrocatalytic Oxidation of Nicotinamide Adenine Dinucleotide (NADH)
			3.3.1 V‐containing POMs as Electrocatalysts in Homogeneous Phase
			3.3.2 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Layer‐by‐layer and Precipitate‐deposition‐modified Electrodes
			3.3.3 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Layer‐by‐layer and Nanoparticle‐modified Electrodes
			3.3.4 POM‐containing Hybrids as Electrocatalysts in Heterogeneous Phase: Precipitate‐deposition‐modified Electrodes and Electro‐generated Chemiluminescence
			3.3.5 POMs in Artificial Reductase Systems for Oxidation Catalysis
		3.4 Conclusion
		List of Abbreviations
		References
	4. POM-based Electrocatalysts for Pharmaceutical Molecules Oxidation
		4.1 Introduction
		4.2 Preparation Methods of POM‐based Films and (Nano)composites
		4.3 POM‐based Electrocatalysis
			4.3.1 Electrocatalysis
			4.3.2 Dopamine Oxidation
			4.3.3 Ascorbic Acid Oxidation
			4.3.4 Other Molecules
		4.4 Conclusions
		Acknowledgments
		List of Abbreviations
		References
Part III. Polyoxometalates for Reductive Electrocatalysis
	5. POM‐based Electrocatalysts for Inorganic Water Contaminants and Hydrogen Peroxide Reduction
		5.1 Introduction
		5.2 Nitrite Reduction
		5.3 Bromate Reduction
		5.4 Iodate Reduction
		5.5 Hydrogen Peroxide Reduction Reaction
		5.6 Conclusions
		Acknowledgment
		List of Abbreviations
		References
	6. POM-based Electrocatalysts for Carbon Dioxide Reduction
		6.1 Introduction
		6.2 Thermodynamics of CO2 Reduction
		6.3 Appealing Properties of POMs for CO2 Reduction
			6.3.1 A Reservoir of ‘Hopping’ Electrons
			6.3.2 Proton‐coupled Electron Transfer in POMs
			6.3.3 Tuning of the Reducibility of the POMs
			6.3.4 Massive Electron Storage in POMs
			6.3.5 A Versatile Platform
		6.4 Coordination of CO2 by POM Compounds
		6.5 Electrocatalytic Reduction of CO2 with Dissolved POMs
			6.5.1 3D Transition‐metal‐substituted POMs as Electrocatalysts in Organic Solvents
			6.5.2 Platinoid‐containing Hybrid POMs as Electrocatalysts in Organic Solvents
			6.5.3 POMs as Electron Relays in Aqueous Solution
		6.6 Electrocatalytic Reduction of CO2 at POMs‐modified (Semi)conducting Electrode Surfaces
			6.6.1 Immobilization of POMs on Electrodes
			6.6.2 POMs‐modified Electrodes Electrocatalytically Active for CO2 Reduction
		6.7 Conclusions
		References
Part IV. Polyoxometales for Fuel Cells and Electrolysers
	7. POM‐based Electrocatalysts for Oxygen Evolution Reaction
		7.1 Introduction: The OER Process
		7.2 Pure POMs as OER Electrocatalysts
			7.2.1 Structural and Mechanistic Considerations
				7.2.1.1 POMs as Platforms for Water Oxidation Electrocatalysis
				7.2.1.2 Water Oxidation Mechanism of POMs
			7.2.2 Homogeneous Electrocatalysis
			7.2.3 Heterogeneous Electrocatalysis
		7.3 POM‐containing (Nano)composites as OER Electrocatalysts
			7.3.1 POM/Carbon (Nano)composites
			7.3.2 POMs Combined with Metals/Metal Oxides/Metal Hydroxides/Metal Complexes
			7.3.3 POM/MOF Nanocomposites
			7.3.4 Other Nanomaterials
		7.4 Heterogeneous Materials Derived from POM and POM‐containing Nanocomposites
			7.4.1 Encapsulation of POMs into MOFs Structures as Precursors for WO Electrocatalysts
			7.4.2 Other POM‐based Materials
		7.5 Concluding Remarks
		Acknowledgements
		List of Abbreviations
		References
	8. POM-based Electrocatalysts for Hydrogen Evolution Reaction
		8.1 Introduction: HER Process
		8.2 Pure POMs as HER Electrocatalysts
		8.3 Composite/Hybrid Materials
			8.3.1 Carbon/POM
			8.3.2 MOF/POM (POMOFs)
			8.3.3 Transition‐metal/POM Composites
			8.3.4 Polymer/POM
		8.4 POM‐derived Electrocatalysts
			8.4.1 SACs
			8.4.2 Transition‐metal Carbides
			8.4.3 Transition‐metal Chalcogens
			8.4.4 Transition‐metal Nitrates
			8.4.5 Transition‐metal Phosphides
			8.4.6 Transition‐metal Oxides
		8.5 Concluding Remarks
		Acknowledgements
		List of Abbreviations
		List of Symbols
		References
	9. POM-based Electrocatalysts for Oxygen Reduction Reactions
		9.1 Introduction
		9.2 Fundamentals of Oxygen Reduction Reaction
		9.3 State‐of‐the‐Art Electrocatalysts for the ORR
		9.4 POM‐based Electrocatalysts for the ORR
		9.5 Conclusions
		Acknowledgements
		References
Part V. Polyoxometales for Batteries and Supercapacitors
	10. POM‐based Nanomaterials for Battery Applications
		10.1 Introduction
		10.2 Criteria for Efficient Redox Flow Batteries
		10.3 Electrolyte Requirements for Redox Flow Batteries (RFBs)
			10.3.1 Wide Potential Window
			10.3.2 Energy Density and High Solubility
			10.3.3 Fast Electron‐transfer Kinetics
			10.3.4 High Ionic Conductivity
			10.3.5 Mass Transfer and Viscosity of Electrolyte
			10.3.6 Long‐term Stability of Active Materials
			10.3.7 Costs and Safety
		10.4 Classification of POMs
		10.5 Suitability of POMs for Energy Conversion and Storage Devices
			10.5.1 POMs in Supercapacitors
			10.5.2 POMs in Li‐ion Batteries
			10.5.3 POMs in Na‐ion Batteries
			10.5.4 POMs in RFBs
		10.6 Further Possibilities
		10.7 POM‐based RFBs in Comparison with Other RFBs
			10.7.1 Iron/Chromium RFBs
			10.7.2 All‐vanadium RFBs
			10.7.3 Zn/Br2 RFBs
		10.8 Conclusions
		Abbreviations and Symbols
		References
	11. POM-based Nanomaterials for Supercapacitors
		11.1 Introduction to Energy‐storage Devices
		11.2 Properties of POMs for Supercapacitors
			11.2.1 POMs as Electrode Materials
				11.2.1.1 POM/Carbon Composites
				11.2.1.2 POMs into Conductive Polymers
				11.2.1.3 POM‐based Ternary Nanohybrids (TNH)
				11.2.1.4 POMs Within Supramolecular Structures
			11.2.2 POMs as Electrolyte Additives
		11.3 Conclusions and Future Perspectives
		Acknowledgements
		References
Index