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ÊéÃûHeterogeneous Photocatalysis Using Inorganic
Semiconductor Solids
×÷ÕßUmar Ibrahim Gaya
Ò³Êý222
³ö°æÉçspringer
ISBN 978-94-007-7774-3 ISBN
1 Principles of Heterogeneous Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Background Sketch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Evolution of Semiconductor Photocatalysis . . . . . . . . . . . . . . . . . . . . . 6
1.3 Photophysics and Photochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Band Gap Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 Semiconductivity and Energetics . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.3 Defects in Semiconductor Solids . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.4 Photoactivation of Semiconductors . . . . . . . . . . . . . . . . . . . . . . 14
1.3.5 Band Gap Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.4 Photocatalytic Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5 Chemistry of the Inception Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.5.1 Charge Carrier Trapping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.5.2 Primary Electron and Hole Transfer Reactions . . . . . . . . . . . . 23
1.6 Roles of Reactive Oxidising Species . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.6.1 Influence of Hole Juxtaposed to Hydroxyl Radical . . . . . . . . . 25
1.6.2 Superoxide Radical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.6.3 Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.6.4 Singlet Molecular Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.7 The Fate of Inorganic and Organic Contaminants . . . . . . . . . . . . . . . . 30
1.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2 Kinetic Concepts of Heterogeneous Photocatalysis . . . . . . . . . . . . . . . . . 43
2.1 Background Sketch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2 Decay Models in Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3 Pseudo Order Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.4 Fractional Lifetimes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.5 Manifestations of Second Order Decay Kinetics in Photocatalysis . . 50
2.6 Finding Order and Rate Constant From Graphic Profiles . . . . . . . . . . 53
2.6.1 Integrated Rate Law Method for Single Reactant . . . . . . . . . . 54
2.6.2 Initial rate method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.6.3 Initial Rate Ratio Method (For Mixed Reactants) . . . . . . . . . . 55
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  • ¸½¼þ 1 : Umar_Ibrahim_Gaya_(auth.)-Heterogeneous_Photocatalysis_Using_Inorganic_Semi.pdf
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