Energy Resources through Photochemistry and Catalysis

ContributorsPreface1. Light-Induced and Thermal Electron-Transfer Reactions I. Introduction II. Kinetic Formulation III. Classical Approach to Electron-Transfer Reactions IV. Quantum Mechanical Approach to Electron-Transfer Reactions V. Comparison between the Classical and Quantum Mechanical Models VI. Peculiar Features of Electronically Excited States as Reactants in Electron-Transfer Processes VII. Correlations of Rate Constants VIII. Discussion of Selected Experimental Results IX. Conclusion References2. Dynamics of Light-Induced Energy and Electron Transfer in Organized Assemblies I. Introduction II. General Consideration of Organized Structure III. Kinetic Processes in Micellar Media IV. Kinetics in Other Organized Assemblies V. Conclusion References3. Molecular Engineering in Photo-conversion Systems I. Introduction II. Self-Organization and Light-Induced Charge Separation in Solutions of Amphiphilic Redox Chromophores III. Water-Cleavage Cycles and Development of Artificial Analogs of Photosystem II of Green Plants IV. Colloidal Semiconductors V. Conclusions References4. Photocatalytic Water Reduction to H2: Principles of Redox Catalysis by Colloidal-Metal "Microelectrodes" I. Introduction II. The Electrochemical Model III. A Simple Electrochemical Theory IV. Quantitative Aspects V. Preparation and Characterization of Active Metal Colloids VI. Assays of Activity for H20 Reduction VII. Experimental Results VIII. Related Systems Appendix: Equations for Current-Potential Curves as Applied to Heterogeneous Catalysis References5. Development of Molecular Photocatalytic Systems for Solar-Energy Conversion: Catalysts for Oxygen and Hydrogen Evolution from Water I. Introduction II. Hydrogen Evolution from Water III. Oxygen Evolution from Water IV. Photochemical Charge Separation References6. The Role of Porphyrins in Natural and Artificial Photosynthesis I. Introduction II. Photosynthesis III. Light Harvesting IV. Charge Separation V. Charge Transport VI. Oxygen Formation VII. Fuel Production VIII. Conclusions References7. Semiconductor Particulate Systems for Photocatalysis and Photosynthesis: An Overview I. Introduction II. Photoprocesses with "Naked" Semiconductor Powder Dispersions III. Photoprocesses with "Metalized" Semiconductor Powder Dispersions IV. Photoprocesses in Semiconductor Dispersions Loaded with Oxides: Hole Transfer and Bi-functional Catalysis V. Semiconductor Dispersions as "Carriers" of Catalysts and Photosensitizers VI. Physical Methods in the Study of Semiconductor Dispersions and Colloids VII. Addendum References8. Bi-functional Redox Catalysis: Synthesis and Operation in Water-Cleavage Reactions I. Introduction II. Required Properties for Efficient Colloidal Semiconductors III. Preparation and Characteristics of Colloidal Titanium Dioxide IV. Photoinduced Redox Reactions V. Colloidal Redox Catalysts VI. Cyclic Water Cleavage with Bi-functional Redox Catalysts VII. Increasing the Efficiency and the Sunlight Response VII. Outlook References9. Examples for Photogeneration of Hydrogen and Oxygen from Water I. Evolutions of H2 Induced by Visible Light in Sacrificial Systems II. Evolution of O2 in Dark- and Light-Induced Processes in Sacrificial Systems III. Hydrogen Evolution Induced by Light-Catalyzed Colloidal TiO2-Loaded Systems IV. Design of Spinel- and Perovskite-Type Semiconductors Active in H2 Evolution Induced by Visible Light References10. Photosynthesis and Photocatalysis with Semiconductor Powders I. Introduction II. Photocatalytic Effect of Semiconductors III. Photoassisted Decomposition of Water with Powdered Semiconductors IV. Hydrogen Production from the Photocatalytic Reaction of Water and Organic Compounds V. Hydrogen Production by Visible Light VI. Energy Structure of the Ti02-Pt Particle and Its Photocatalytic Activity VII. Application of Photocatalytic Reaction to Organic Synthesis VIII. Summary References11. Photoelectrolysis of Water and Sensitization of Semiconductors I. Introduction II. Photoelectrolysis of Water with Semiconductors III. Sensitization of Semiconductors: Chlorophyll-Sensitized Semiconductor Electrodes References12. Hydrogen-Generating Solar Cells Based on Platinum-Group Metal Activated Photocathodes I. Scope II. Requirements for Efficient Solar Hydrogen Generation III. Solar Conversion Efficiency IV. Chemical Stability of the Photocathode-Solution Interface V. Radiationless Recombination of Photogenerated Electrons at the Photocathode-Electrolyte Interface VI. The Relationship between the Fill Factor and the Overvoltage in Hydrogen-Evolving Solar Cells VII. The Relationship between the Barrier Height and the Gain in Threshold Potential for Hydrogen Evolution VIII. Stability of the Solar Conversion Efficiency IX. Photoelectrolysis at High Levels of Irradiance X. Photoelectrolytic Cells with p-lnP (Rh, H Alloy) Photocathodes XI. Spontaneous Two-Photon Photoelectrolysis of HBr XII. Conclusions References13. Photoelectrochemistry of Cadmium and Other Metal Chalcogenides in Polysulfide Electrolytes I. Introduction II. Interaction between CdS and Sulfide Ions in Solution III. Stability of the CdSe-Polysulfide System IV. Other Cadmium Chalcogenide-Polysulfide Systems V. Zinc (and Zinc-Cadmium) Chalcogenides VI. Other Metal Chalcogenides VII. Polyselenide and Polytelluride Electrolytes VIII. Surface Treatment of CdX Photoelectrodes References14. Electrically Conductive Polymer Layers on Semiconductor Electrodes I. Introduction II. Photoelectrochemical Devices: Principles and Definitions III. Instability of n-Type Semiconductor Electrodes IV. Experimental Considerations V. Transport Properties VI. Electrochemical Photovoltaic Cells VII. Surface States and Interface Energetics VIII. Photoelectrolysis of Water IX. Guidelines for Control of Interface References15. Photochemical Fixation of Carbon Dioxide I. Introduction II. Energetics of Carbon Dioxide Reduction III. Photochemical Fixation of Carbon Dioxide IV. Electrochemical Reduction of Carbon Dioxide V. Dynamics of Carbon Dioxide Reduction VI. Photoelectrochemical Reduction of Carbon Dioxide VII. Photoreduction of Carbon Dioxide with Semiconductors VIII. Conclusions References16. Catalytic Nitrogen Fixation in Solution I. Introduction II. Peculiarities of the Thermodynamics of Molecular Nitrogen Reduction III. Nitrogen Reduction in Aprotic Media IV. Molecular Nitrogen Complexes with Transition-Metal Compounds and the Mechanism of Nitrogen Reduction in the Coordination Sphere of the Complex V. Nitrogen Reduction in Protic Media VI. Conclusion ReferencesIndex