Oxygen Reduction Reaction: Fundamentals, Materials, and Applications

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Oxygen Reduction Reaction: Fundamentals, Materials and Applications covers the design, synthesis and performance efficacies of the entire spectrum of oxygen reduction catalysts, extrapolating down to their applications in practical, alternative, renewable energy devices. Catalysts covered include heme inspired iron-based, heme inspired non-iron-based, non-heme-based, noble metal-based, non-noble metal-based and metal-free homogeneous and heterogeneous catalysts. The book contains critical analyses and opinions from experts around the world, making it of interest to scientists, engineers, industrialists, entrepreneurs and students. Cover Half Title Oxygen Reduction Reaction: Fundamentals, Materials, and Applications Copyright Contents Contributors About the editors Preface Foreword Acknowledgments 1. Oxygen reduction reaction in nature and its importance in life 1.1 Introduction to oxygen reduction reaction: Background and significance 1.2. Oxygen activation and oxygen reduction reaction 1.3. Oxygen reduction catalyzed by metalloenzymes: A close look into the structure-function relationship 1.3.1. Cytochrome oxidase 1.3.2. Multicopper oxidase 1.4. Natural and artificial metalloprotein models as ORR catalysts 1.5. Oxygen reduction reaction by bio-inspired synthetic catalysts 1.5.1. Homogenous molecular electrocatalysts 1.5.1.1. Porphyrin-based electrocatalysts 1.5.1.2. Non-porphyrin homogeneous molecular electrocatalysts 1.5.2. Heterogenous molecular electrocatalysts 1.5.2.1. Porphyrin-based electrocatalysts 1.5.2.2. Copper-based heterogenous electrocatalysts 1.6. The future of oxygen activation: Summary and outlook References 2. Oxygen reduction reaction by metalloporphyrins 2.1 Introduction 2.2 The porphyrin cofactor 2.3. Common methods used in the study of O2 reduction reaction 2.3.1. ORR in solution 2.3.2. ORR on electrodes 2.4. Different metalloporphyrins as ORR catalysts 2.4.1. Iron porphyrins 2.4.2. Cobalt porphyrins 2.4.3. Other metalloporphyrins 2.5. Porphyrin-based frameworks for ORR 2.6. Metal-free porphyrins 2.7. Future direction of oxygen reduction by porphyrins References 3. Oxygen reduction reaction by metallocorroles and metallophthalocyanines 3.1 Introduction 3.2 Different routes of ORR 3.3 Advantages of phthalocyanine and corroles for ORR 3.4. Metallocorroles as ORR catalysts 3.4.1. Dyads 3.4.1.1. Porphyrin(P)-corrole (C) dyads (PYC) Effect of spacers Effect of meso-substitution of the corrole Effect of heterometallation in the porphyrin 3.4.1.2. Corrole(C)-corrole(C) dyads (CYC) 3.4.2. Monomeric cobalt(III) corroles 3.4.2.1. Mono meso-substituted corrole 3.4.2.2. Tri mes-substituted corrole With ortho-substitution at meso-aryl group Para-aryl substitution β-Pyrrole substation 3.4.3. Hangman corrole 3.4.4. Monomeric cobalt corrole attached to carbon nanotubes 3.4.5. Other metallocorroles for ORR study 3.5. Metal complexes of phthalocyanine as ORR catalyst 3.5.1. Iron phthalocyanine (FePc) complex for ORR 3.5.1.1. Monomeric iron phthalocyanine complex for oxygen reduction reaction 3.5.1.2. Homo- and hetero-dinuclear phthalocyanines for oxygen reduction reaction 3.5.1.3. Phthalocyanine-porphyrin-based polymers for oxygen reduction reaction 3.5.1.4. Phthalocyanine with graphitic carbon and carbon nanotube conjugate (FePc-CNTs) in oxygen reduction reaction 3.5.1.5. Phthalocyanine with graphene and graphene oxide conjugate (FePc) in oxygen reduction 3.5.2. Cobalt phthalocyanine (CoPc) complex for oxygen reduction reaction 3.5.3. Other metallophthalocyanine (MPc) complexes for oxygen reduction reaction 3.6. Summary and future prospect Acknowledgments References 4. Oxygen reduction reaction by metal complexes containing non-macrocyclic ligands 4.1 Introduction 4.2 Reactivity 4.2.1. Homogenous studies 4.2.1.1. Manganese-based catalysts 4.2.1.2. Iron-based catalysts 4.2.1.3. Cobalt based catalysts 4.2.1.4. Copper-based catalysts 4.2.2. Electrocatalytic studies 4.2.2.1. Manganese electrocatalysts 4.2.2.2. Iron electrocatalysts 4.2.2.3. Cobalt electrocatalysts 4.2.2.4. Nickel electrocatalysts 4.2.2.5. Copper electrocatalysts 4.2.3. Oxygen reduction by polyoxometalates 4.2.3.1. Polyoxometalate as soluble molecular catalyst oxygen reduction reaction 4.2.3.2. Polyoxometalate as catalyst for cathodic O2 reduction in fuel cell 4.3. Summary and outlook References 5. Oxygen reduction reaction by noble metal-based catalysts 5.1 Introduction 5.2 Analytical methods to assess ORR 5.3 Standard protocols for obtaining data with Pt/C 5.4. Mono- and multi-metallic catalysts 5.4.1. Platinum (Pt) 5.4.2. Palladium (Pd) 5.4.3. Gold (Au) 5.4.4. Ruthenium (Ru) 5.4.5. Osmium (Os) 5.4.6. Rhodium (Rh) 5.4.7. Silver (Ag) 5.4.8. Iridium (Ir) 5.5. Alloy-based catalysts 5.6. Metal oxides catalysts 5.7. Photocatalytic oxygen reduction reaction 5.8. Direct synthesis of hydrogen peroxide on transition metal surface 5.9. Noble metals in aerobic oxidation reactions 5.10. Commercial and environmental viability 5.11. Summary and future directions References 6. Oxygen reduction reaction by non-noble metal-based catalysts 6.1 Introduction 6.2 ORR mechanism 6.3 Oxygen reduction reaction kinetics 6.4 Single and dual metal sites-based single atomic catalyst 6.5 Alloy-based catalysts 6.6. Metal oxides catalysts 6.6.1. Single transition metal oxides-type catalysts 6.6.2. Perovskite-type catalysts 6.6.3. Spinel-type catalysts 6.6.4. Other ternary transition metal oxides 6.7. Transition metal chalcogenides 6.8. Transition metal carbides/nitrides/oxynitrides 6.8.1. Transition metal carbides 6.8.2. Transition metal nitrides 6.8.3. Transition metal oxynitrides 6.9. Commercial and environmental viability 6.10. Summary and future directions Acknowledgments References 7. Oxygen reduction reaction by metal-free catalysts 7.1 Introduction 7.2 Synthesis and synergistic effects of dopants 7.3 Carbon nanotube-based catalysts 7.4 Graphene-based catalysts 7.5 Graphite or graphitic nanoplatelet-based catalysts 7.6 3D porous carbon catalysts 7.7. Other carbon material catalysts 7.7.1. Single atom-doped carbon materials 7.7.1.1. N-doped carbon catalysts 7.7.1.2. P-doped carbon catalysts 7.7.1.3. B-doped carbon catalysts 7.7.1.4. Si-doped carbon catalysts 7.7.1.5. S-doped carbon catalysts 7.7.1.6. Halogen-doped carbon catalysts 7.7.2. Codoped carbon materials 7.8. Commercial and environmental viability Acknowledgments References 8. Oxygen reduction reaction in hydrogen fuel cells 8.1 Introduction 8.2. Fundamental concept and working principle 8.2.1. Actual performance 8.2.1.1. Activation-related losses 8.2.1.2. Ohmic losses 8.2.1.3. Mass-transport-related losses 8.2.1.4. Cell voltage 8.2.1.5. Fuel cell assembly 8.3. Catalyst materials used: Design, synthesis, and performances 8.3.1. Design 8.3.1.1. Choice of catalyst 8.3.2. Synthesis 8.3.3. Performances 8.4. Commercial and environmental viability 8.4.1. Commercial viability 8.4.2. Environmental viability 8.5. Existing challenges and future direction 8.5.1. Cost 8.5.2. Degradation 8.6. Summary References Further reading 9. Oxygen reduction reaction in methanol fuel cells 9.1 Introduction: Background and significance 9.2 Direct methanol fuel cells (DMFCs) 9.2.1 Fundamental concepts and working principle 9.2.1.1. Methanol oxidation reaction (MOR) catalyst 9.2.1.2. Membranes for DMFC 9.2.1.3. Oxygen reduction reaction (ORR) 9.3. ORR catalysts in DMFC: Design, synthesis, and performance 9.3.1. Pt-based ORR catalyst 9.3.2. Other metallic electrodes 9.3.3. Transition metal oxides 9.3.4. Ternary transition metal oxides 9.3.5. Transition metal dichalcogenides 9.3.6. Transition metal nitrides 9.3.7. Transition metal carbides 9.3.8. Carbon nanomaterials 9.3.9. Metal-organic frameworks (MOFs) 9.4. Commercial and environmental viability of the catalyst materials 9.5. Existing challenges and future directions 9.6. Summary Acknowledgments References Further reading 10. Oxygen reduction reaction in ethanol fuel cells 10.1 Introduction 10.2. Fundamental concepts and working principle 10.2.1. Working principle of DEFC 10.2.1.1. PEM based DEFC 10.2.1.2. AEM based DEFC 10.2.1.3. AAEM-based DEFC 10.2.2. Fundamental concepts 10.2.2.1. Ethanol energy density 10.2.2.2. Ethanol crossover 10.2.2.3. Thermodynamics and kinetics Ethanol oxidation Oxygen reduction reaction 10.3. Cathode catalysts 10.3.1. Platinum catalysts 10.3.1.1. Bimetallic alloys 10.3.1.2. Trimetallic alloys 10.3.2. Palladium-based catalysts 10.3.2.1. Bimetallic alloys 10.3.2.2. Trimetallic alloys 10.3.3. Ru based electrocatalysts 10.3.4. Non-noble metal based electrocatalysts 10.3.4.1. Molecular systems 10.3.4.2. Heterogenous M-N-C catalysts (metal and heteroatom doped carbon nanostructures) Synthetic methodology Application of M-N-C catalysts in alcohol fuel cells 10.4. Commercial and environmental viability of the catalyst materials 10.5. Existing challenges and future directions 10.6. Summary References 11. Oxygen reduction reaction in solid oxide fuel cells 11.1 Background and significance 11.2. Fundamental concepts and working principle 11.2.1. Thermodynamics and kinetics 11.2.2. Materials 11.2.2.1. Solid electrolyte 11.2.3. Oxygen vacancy concentration 11.2.4. Oxide ions flux 11.2.5. Cell designs for measuring overpotentials 11.2.6. MEA architectures 11.2.7. SOFC testing 11.2.8. Electrochemical impedance spectroscopy (EIS) 11.3. Catalyst materials for oxygen reduction reaction 11.3.1. Catalyst materials 11.3.1.1. Perovskites (ABO3) 'A' Site substituted ABO3 'B' Site substituted ABO3 11.3.1.2. Double perovskites (A2B2O6-δ) 11.3.1.3. Ruddlesden-Popper phase (An+1BnO3n+1; n=1, 2, 3) 11.3.1.4. Non-perovskite materials Pyrochlores 11.3.1.5. Phases with tetrahedrally coordinated cobalt 11.3.1.6. Other structure types 11.4. Methods used for preparation of cathode catalyst 11.4.1. Solid-state synthesis 11.4.2. Hydrothermal synthesis 11.4.3. Co-precipitation method 11.4.4. Sol-gel method 11.4.5. Combustion synthesis 11.5. Method used for catalyst deposition on electrolytes 11.5.1. Thin-film deposition 11.5.2. Tape casting 11.5.3. Screen printing 11.5.4. Other thin film deposition methods 11.5.5. Infiltration 11.5.6. Exsolution 11.6. Commercial and environmental viability of the catalyst materials 11.7. Challenges and future directions 11.7.1. Environmental factors (reactive instability) 11.7.1.1. Stability in H2O 11.7.1.2. Stability in CO2 11.7.1.3. Cr poisoning 11.7.1.4. Segregation of ions 11.7.1.5. Interfacial phase formation References 12. Oxygen reduction reaction in enzymatic biofuel cells 12.1 Introduction 12.2 Basic features: Kinetics and thermodynamics 12.3 Immobilization of enzymes onto electrodes for electronic coupling 12.4. Enzymatic O2 reduction 12.4.1. Electrocatalytic O2 reduction by laccases 12.4.2. Bilirubin oxidases (BODs) 12.4.3. Cytochrome c and cytochrome oxidase 12.5. Application of EBFCs 12.5.1. Implantable devices 12.5.2. Wearable devices 12.5.3. Detection of biological metabolites under in-vivo condition 12.6. Conclusion and outlook Acknowledgment References 13. Oxygen reduction reaction in lithium-air batteries 13.1 Introduction: Background and significance 13.2. Fundamental aspects of LABs 13.2.1. Cathodic ORR in various LABs 13.2.2. Cathodic ORR mechanisms in LABs 13.3. Catalyst materials 13.3.1. Design of cathode materials and their performance 13.3.1.1. Precious metals and/or their oxides 13.3.1.2. Manganese oxides 13.3.1.3. Transition metals and/or their oxides 13.3.1.4. Perovskites and related oxides 13.3.2. Composite materials 13.3.3. Other cathode materials 13.4. Commercial and environmental viabilities of catalyst materials 13.5. Summary, existing challenges and future directions References Index Cover back