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A surface science perspective on View the MathML source photocatalysis Michael A. Henderson Corresponding Author Contact Information, a, E-mail The Corresponding Author a Institute for Interfacial Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, MS K8-87, Richland, WA 99352, United States Received 9 February 2010; Accepted 25 January 2011. editor: W.H. Weinberg. Available online 6 May 2011. Abstract The field of surface science provides a unique approach to understanding bulk, surface and interfacial phenomena occurring during TiO2 photocatalysis. This review highlights, from a surface science perspective, recent literature that provides molecular-level insights into photon-initiated events occurring at TiO2 surfaces. Seven key scientific issues are identified in the organization of this review. These are: (1) photon absorption, (2) charge transport and trapping, (3) electron transfer dynamics, (4) the adsorbed state, (5) mechanisms, (6) poisons and promoters, and (7) phase and form. This review ends with a brief examination of several chemical processes (such as water splitting) in which TiO2 photocatalysis has made significant contributions in the literature. Keywords: TiO2 photocatalysis Article Outline 0. Introduction 1. Photon absorption 1.1. Pure TiO2 1.2. Nanoscaled TiO2 1.3. Surface absorption effects 1.3.1. Surface states 1.3.2. Surface modification 1.3.3. Doping 2. Charge transport and trapping 2.1. Exciton transport and trapping 2.2. Charge separation and thermalization 2.3. Charge transport 2.3.1. Carrier effective mass 2.3.2. Electron transport 2.3.3. Hole transport 2.4. Charge trapping 2.4.1. Electron trapping 2.4.2. Hole trapping 2.5. Charge recombination 2.5.1. Radiative 2.5.2. Non-radiative 3. Electron transfer dynamics 3.1. Excited electron donor to TiO2 conduction band 3.2. Electron donor to TiO2 valence band hole 3.3. TiO2 conduction band to electron acceptor 3.4. TiO2 valence band to acceptor hole 4. Adsorption and the adsorbed state 4.1. Structure sensitivity 4.2. Coverage dependence 5. Mechanisms 5.1. General issues 5.1.1. Direct versus indirect events 5.1.2. Overall rates and quantum efficiencies 5.1.3. Lattice oxygen 5.1.4. Photoadsorption and photodesorption 5.1.5. Surface defect formation 5.2. Photooxidation reactions 5.2.1. Electron scavengers: View the MathML source 5.2.2. Electron scavengers: others 5.2.3. Photooxidation reactants 5.3. Photoreduction reactions 5.3.1. Hole scavengers 5.3.2. Photoreduction reactants 6. Poisons and promoters 6.1. Noble metals 6.2. Acidic and basic conditions 6.3. Water 6.3.1. Inhibitor 6.3.2. Promoter 6.4. Oxide additives 6.4.1. Physical effects 6.4.2. Chemical effects 6.4.3. Electronic effects 6.5. Metal cations 6.6. Miscellaneous poisons and promoters 6.6.1. Self-poisoning 6.6.2. Reaction product/intermediate poisoning 6.6.3. Oxyanions 6.6.4. Halides 6.6.5. Sensitizers 6.6.6. Surface functionalizers 6.6.7. Carbon nanotubes 7. Phase and form 7.1. Phase 7.1.1. Crystalline versus amorphous 7.1.2. Anatase versus rutile 7.1.3. Mixed-phase 7.1.4. Brookite 7.1.5. Tetrahedral TiO2 7.2. Form 7.2.1. Particle surfaces 7.2.2. Surfaces of novel TiO2 materials 7.2.3. Single crystal surfaces 7.2.3.1. Rutile surfaces 7.2.3.2. Anatase surfaces 7.2.3.3. Surface defects 8. Special situations 8.1. Water splitting 8.1.1. Water oxidation 8.1.2. Water reduction 8.2. View the MathML source photoreduction 8.3. Bactericide 8.4. Photoinduced hydrophilicity 8.5. Synthesis by photons 9. Conclusions Acknowledgments References |
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