
Energy Resources through Photochemistry and Catalysis
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Energy Resources through Photochemistry and Catalysis reviews the state of the art in the development of energy conversion devices based on catalytic and photochemical reactions. The focus is on catalysis of redox reactions and their application to the photocleavage of water, reduction of carbon dioxide, and fixation of nitrogen. Some fundamental aspects of catalysis as it relates to processes of light energy harvesting and charge separation in photochemical or photoelectrochemical conversion systems are also discussed. This monograph is comprised of 16 chapters covering light-induced redox reactions and reaction dynamics in organized assemblies such as micelles, colloidal metals, or semiconductors, together with strategies for molecular engineering of artificial photosynthetic devices. The principles of electrochemical conversion of light energy via semiconductor electrodes or semiconducting particles are also considered. Furthermore, thermodynamic characteristics for some reactions that can be utilized for storage of solar energy in the form of chemical energy are examined. The remaining chapters look at the role of porphyrins in natural and artificial photosynthesis; the use of semiconductor powders and particulate systems for photocatalysis and photosynthesis; and hydrogen-generating solar cells based on platinum-group metal activated photocathodes. This text will be a useful resource for scientists and policymakers concerned with finding alternative sources of energy.
Table of Contents
Contributors
Preface
1. 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
References
2. 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
References
3. 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
References
4. 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
References
5. 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
References
6. 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
References
7. 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
References
8. 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
References
9. 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
References
10. 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
References
11. Photoelectrolysis of Water and Sensitization of Semiconductors
I. Introduction
II. Photoelectrolysis of Water with Semiconductors
III. Sensitization of Semiconductors: Chlorophyll-Sensitized Semiconductor Electrodes
References
12. 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
References
13. 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
References
14. 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
References
15. 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
References
16. 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
References
Index
Product details
- No. of pages: 588
- Language: English
- Copyright: © Academic Press 1983
- Published: October 28, 1983
- Imprint: Academic Press
- eBook ISBN: 9780323145145
About the Editor
Michael Gratzel
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