Nowotny J. Oxide semiconductors for solar energy conversion: titanium dioxide. - Boca Raton: CRC Press, 2012. - xxx, 393 p.: ill. - (Green chemistry and chemical engineering). - Incl. bibl. ref. - Ind.: p.385-393. - ISBN 978-1-4398-4839-5  Место хранения:   026 | Институт физики полупроводников СО РАН | Новосибирск | Библиотека

Оглавление / Contents

Series Preface ............................................... xiii Foreword ....................................................... xv Foreword ..................................................... xvii Preface ....................................................... xix Notation .................................................... xxiii Introduction ................................................ xxvii Chapter 1 Solid-State Electrochemistry of Binary Metal Oxides .. 1 1.1 Structural Defects ......................................... 1 1.1.1 Thermodynamically Irreversible Defects .............. 1 1.1.2 Point Defects ....................................... 4 1.2 Nonstoichiometry ........................................... 4 1.3 Point Defects in Binary Metal Oxides ....................... 6 1.3.1 Types of Defects .................................... 6 1.3.2 Thermodynamic Approach .............................. 8 1.3.3 Defect Reactions .................................... 9 1.3.3.1 General Rules .............................. 9 1.3.3.2 Defect Equilibria .......................... 9 1.3.3.3 Stoichiometric Oxides ..................... 11 1.3.3.4 Nonstoichiometric Oxides .................. 12 1.3.3.5 Brouwer-Type Diagrams ..................... 15 1.3.3.6 Effect of Aliovalent Ions (Donors and Acceptors) ................................ 16 1.3.4 Defects Aggregation ................................ 27 1.3.5 Dispersed Systems .................................. 29 1.4 Band Model ................................................ 31 1.5 Electrical Properties ..................................... 36 1.5.1 Electrical Conductivity ............................ 38 1.5.1.1 Effect of Oxygen Activity ................. 38 1.5.1.2 Effect of Temperature ..................... 42 1.5.1.3 Transference Numbers ...................... 44 1.5.1.4 Impedance Spectroscopy .................... 45 1.5.2 Thermoelectric Power ............................... 45 1.5.3 Electrical Conductivity versus Thermoelectric Power Jonker Analysis .............................. 51 1.5.4 Work Function ...................................... 53 1.5.4.1 Basic Terms ............................... 53 1.5.4.2 Work Function at Elevated Temperatures .... 57 1.5.5 Surface Photovoltage Spectroscopy .................. 62 1.5.6 Hall Effect ........................................ 62 1.5.7 Coulometric Titration .............................. 63 1.6 Effect of Interfaces ...................................... 65 1.6.1 Surface Reactivity ................................. 65 1.6.2 Surface Sensitive Tools ............................ 67 1.6.3 Surface Segregation ................................ 69 1.6.3.1 Impurities ................................ 72 1.6.3.2 Low-Dimensional Structures ................ 72 1.6.3.3 Oxygen Activity ........................... 72 1.6.3.4 Segregation of Intrinsic Defects .......... 72 1.6.4 Surface versus Bulk Properties ..................... 73 1.6.4.1 Examples of NiO and CoO ................... 75 1.6.4.2 Examples of NiO and CoO Solid Solutions ... 78 1.6.4.3 Low-Dimensional Interface Structures ...... 86 1.7 Diffusion ................................................. 87 1.7.1 Diffusion Mechanisms ............................... 87 1.7.1.1 Vacancy Mechanism ......................... 87 1.7.1.2 Interstitial Mechanism .................... 87 1.7.1.3 Interstitialcy Mechanism (Collinear) ...... 88 1.7.1.4 Interstitialcy Mechanism (Noncollinear) ... 88 1.7.1.5 Interface Diffusion ....................... 88 1.7.2 Diffusion Kinetics ................................. 89 1.7.3 Grain Boundary Diffusion ........................... 93 1.7.4 Chemical Diffusion ................................. 95 1.7.4.1 Gas/Solid Equilibration ................... 95 1.7.4.2 Bulk Diffusion Controlled Kinetics ........ 99 1.7.4.3 Segregation-Induced Diffusive Resistance ............................... 102 1.7.4.4 Monitoring of Gas/Solid Kinetics ......... 105 1.7.4.5 Relationships between Diffusion Coefficients ............................. 108 1.8 Oxygen Ion Conductors .................................... 110 1.8.1 Electronic versus Ionic Conductors ................ 110 1.8.2 Electrochemical Cells ............................. 110 1.8.3 Oxidation Mechanism ............................... 114 1.9 Brief Survey on Selected Oxides .......................... 117 1.10 Concluding Remarks ....................................... 118 References ............................................... 119 Assignable Problems ...................................... 125 Chapter 2 Light-Induced Effects .............................. 127 2.1 Solar Radiation .......................................... 127 2.2 Solar Energy Spectrum .................................... 127 2.3 Light Source ............................................. 132 2.4 Light-Induced Effects in Semiconductors .................. 132 2.5 Data Reproducibility ..................................... 134 2.6 Energy Conversion Efficiency ............................. 135 2.6.1 Basic Relationships ............................... 135 2.6.2 Energy Losses ..................................... 138 2.6.2.1 Interdependence of Functional Properties .. 139 2.7 Light Measurements ....................................... 140 2.8 Concluding Remarks ....................................... 141 References ............................................... 141 Assignable Problems ...................................... 143 Chapter 3 Basic Properties of TiO2 ........................... 145 3.1 Titanium Oxides .......................................... 145 3.2 Titanium Dioxide ......................................... 145 3.2.1 Occurrence, Application, and Properties ........... 145 3.2.2 Nonstoichiometry .................................. 146 3.2.3 Production ........................................ 147 3.2.4 Structure ......................................... 148 3.2.5 Phase Diagram and Structures ...................... 151 3.2.6 Shear Structures .................................. 153 3.2.7 Electronic Structure .............................. 155 3.2.8 Anisotropy of Rutile .............................. 158 3.2.8.1 Electrical Resistivity ................... 159 3.2.8.2 Diffusion Kinetics ....................... 159 3.3 Concluding Remarks ....................................... 160 References ............................................... 160 Assignable Problems ...................................... 163 Chapter 4 Defect Chemistry ................................... 165 4.1 Undoped Titanium Dioxide ................................. 165 4.1.1 Point Defects in ТiO2 ............................. 165 4.1.2 Nonstoichiometry .................................. 166 4.1.3 Defect Reactions .................................. 167 4.1.4 Brouwer Defect Diagrams ........................... 171 4.1.5 Full Defect Diagram ............................... 175 4.1.6 Anomalies ......................................... 178 4.1.7 Effect of Cooling ................................. 179 4.1.8 Effect of Oxygen on Fermi Level ................... 180 4.2 Doping with Aliovalent Ions .............................. 183 4.2.1 Cations versus Anions ............................. 183 4.2.2 Donor-Doped TiO ................................... 184 4.2.3 Acceptor-Doped ТiO2 ............................... 186 4.3 Reactivity of Titanium Dioxide with Hydrogen ............. 193 4.4 Real Chemical Formula of ТiO2 ............................ 199 4.5 Concluding Remarks ....................................... 202 References ............................................... 203 Assignable Problems ...................................... 205 Chapter 5 Electrical Properties .............................. 207 5.1 Introduction ............................................. 207 5.2 Electrical Conductivity .................................. 207 5.2.1 General ........................................... 207 5.2.2 Undoped TiO ....................................... 208 5.2.2.1 Effect of Oxygen Activity ................ 210 5.2.2.2 Effect of Temperature .................... 216 5.2.2.3 Mobility Terms ........................... 222 5.2.2.4 Transference Numbers ..................... 224 5.2.2.5 Electrical Conductivity Components ....... 226 5.2.2.6 Effect of Impurities ..................... 229 5.2.2.7 Effect of Cooling ........................ 230 5.2.3 Donor-Doped ТiO2 .................................. 232 5.2.4 Acceptor-Doped ТiO2 ............................... 239 5.2.5 Heterogeneous Doping of ТiO2 ...................... 241 5.3 Thermoelectric Power ..................................... 242 5.4 Jonker Analysis .......................................... 255 5.5 Work Function ............................................ 259 5.6 Surface Photovoltage Spectroscopy ........................ 263 5.7 Hall Effect .............................................. 264 5.8 Coulometric Titration .................................... 265 5.9 Concluding Remarks ....................................... 266 References ............................................... 267 Assignable Problems ...................................... 272 Chapter 6 Diffusion .......................................... 275 6.1 Mass Transport Kinetics .................................. 275 6.2 Self-Diffusion ........................................... 275 6.3 Chemical Diffusion ....................................... 280 6.3.1 Equilibration Kinetics ............................ 280 6.3.2 Double Equilibration Kinetics ..................... 286 6.3.3 Nb-dopedTiO ....................................... 288 6.3.4 Alternative Diffusion Models ...................... 291 6.4 Concluding Remarks ....................................... 294 References ............................................... 295 Assignable Problems ...................................... 297 Chapter 7 Effect of Interfaces ............................... 299 7.1 Effect of Surface Properties on Reactivity ............... 299 7.1.1 Introduction ...................................... 299 7.1.2 Surface Science Approach .......................... 299 7.2 Segregation .............................................. 304 7.3 Reactivity ............................................... 309 7.3.1 Reactivity of ТiO2 with Light ..................... 309 7.3.2 Reactivity and Photoreactivity of ТiO2 with Oxygen and Water .................................. 310 7.3.2.1 Oxygen ................................... 310 7.3.2.2 Water .................................... 311 7.3.3 Collective and Local Reactivity Factors ........... 312 7.4 Concluding Remarks ....................................... 318 References ............................................... 317 Assignable Problems ...................................... 322 Chapter 8 Applications ....................................... 323 8.1 Introduction ............................................. 323 8.2 Performance-Related Properties ........................... 324 8.2.1 Electronic Structure .............................. 325 8.2.2 Flat Band Potential ............................... 327 8.2.3 Charge Transport .................................. 330 8.2.4 Surface Active Sites .............................. 330 8.2.5 Surface versus Bulk Properties .................... 331 8.3 Solar Hydrogen ........................................... 332 8.3.1 Solar-to-Hydrogen Pathways ........................ 332 8.3.2 Solar Water Splitting in Nature ................... 334 8.3.3 Environmental Aspects ............................. 335 8.3.4 Cost-Related Aspects .............................. 338 8.4 Hydrogen Generation by Photoelectrochemical Water Splitting ................................................ 338 8.4.1 General Concept ................................... 339 8.4.2 Reactions in Photoelectrochemical Cells ........... 342 8.4.3 Band Model of Photoelectrochemical Cells .......... 343 8.4.4 Photocell Structures .............................. 346 8.4.4.1 Photoelectrochemical Cell Equipped with One Photoelectrode .................. 347 8.4.4.2 Hybrid-Type Cells ........................ 347 8.4.4.3 Photoelectrochemical Cell Equipped with Two Photoelectrodes ................. 349 8.4.4.4 Alternative Solutions .................... 352 8.4.5 Simple Comparisons ................................ 353 8.4.6 Hurdles to Commercialization ...................... 354 8.4.6.1 Potential Market ......................... 354 8.4.6.2 Multidisciplinary Approach ............... 354 8.5 Solar Water Purification ................................. 356 8.5.1 Significance and Basic Concepts ................... 356 8.5.2 Photoreactivity of ТiO2 with Water ................ 358 8.5.2.1 Anodic Site .............................. 358 8.5.2.2 CathodicSite ............................. 360 8.5.3 Modification of Photocatalytic Properties ......... 361 8.5.3.1 Deposition of Noble Metals ............... 361 8.5.3.2 Doping with Aliovalent Ions .............. 362 8.5.4 Unresolved Problems ............................... 362 8.5.5 Oxidation of Microorganisms ....................... 365 8.6 Alternative Applications ................................. 371 8.7 Concluding Remarks ....................................... 372 8.7.1 Research Progress and Perspectives ................ 374 References ............................................... 375 Assignable Problems ...................................... 381 Appendix ...................................................... 383 Fundamental Constants ...................................... 383 Selected Conversion Factors ................................ 383 Selected Definitions ....................................... 383 Conversion Prefixes ........................................ 384 Index ......................................................... 385