Energy Resources through Photochemistry and Catalysis

Energy Resources through Photochemistry and Catalysis

1st Edition - October 28, 1983

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  • Editor: Michael Gratzel
  • eBook ISBN: 9780323145145

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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


    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


    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


    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


    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


    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


    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


    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


    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


    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


    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


    11. Photoelectrolysis of Water and Sensitization of Semiconductors

    I. Introduction

    II. Photoelectrolysis of Water with Semiconductors

    III. Sensitization of Semiconductors: Chlorophyll-Sensitized Semiconductor Electrodes


    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


    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


    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


    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


    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



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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