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Chemical ReviewÉÏ×îÐÂÉÏÏßÁËһƪÃûΪ¡°Titanium Dioxide (Anatase and Rutile): Surface Chemistry, Liquid¨CSolid Interface Chemistry, and Scientific Synthesis of Supported Catalysts¡±µÄ×ÛÊöÎÄÕ£¬×÷ÕßΪKyriakos Bourikas, Christos Kordulis, and Alexis Lycourghiotis £¬È«ÎÄ70Ò³£¬²Î¿¼ÎÄÏ×451ƪ¡£ÕâÆªÎÄÕ±Ƚϳ¤£¬Ð´×÷µÄ½Ç¶È±È½Ï¿í¹ã£¬ÄÚÈÝÒ²±È½ÏÈ«Ãæ£¬»ù±¾ÉϺ­¸ÇÁ˶þÑõ»¯îÑÑо¿µÄ´ó¶àÊý·½Ã棬±ÈÈç¶þÑõ»¯îѵıíÃæ»¯Ñ§ÐÔÖÊ£¬¹ÌÒº½çÃæ·´Ó¦ÐÔÖÊÒÔ¼°ºÏ³É·½ÃæµÄһЩ×ܽᡣ
ÔÚ2014Ä꣬Chemical ReviewÒѾ­¿¯µÇÁ˶þʮƪ×óÓÒÓйضþÑõ»¯îѵÄ×ÛÊö£¬µ«ÊÇ¿´Õâ¸öÑù×Ó£¬¹À¼Æ»¹»áÓв»ÉÙ¶þÑõ»¯îÑ×ÛÊöÔÚÅŶӵȴý·¢±í¡£ËùÒÔ´ÓÕâЩ¿ÉÒÔ¿´³ö£¬µ½Ä¿Ç°À´Ëµ£¬¶þÑõ»¯îÑÒÀÈ»»¹Êǹâ´ß»¯ÁìÓòµÄ×îΪҫÑÛµÄÃ÷Ðǹâ´ß»¯¼Á¡£
1. Introduction
2. Surface Chemistry
2.1. Bulk Structure of the Anatase and Rutile
2.2. Crystal Terminations of Anatase Crystals
2.2.1. Surface Atoms Exposed
2.2.2. Surface Energies before and after Relaxation
2.2.3. Geometrical Surface Relaxations
2.2.4. Surface Reconstructions
2.3. Reactivity of the Anatase Crystal Terminations with Respect to Water Molecules: The Majority (101) Surface
2.3.1. Modes of Adsorption of Isolated Water Molecules on the Perfect (101) Termination
2.3.2. Modes of Adsorption of Water Molecules for Various Temperatures and H2O Surface Concentrations on the Perfect (101) Termination
2.3.3. The Structure of Thin Water Overlayers on the Perfect (101) Termination
2.3.4. Modes of Adsorption of Isolated Water Molecules on the Defective (101) Termination
2.3.5. The Structure of Thin Water Overlayers on the Defective (101) Surface
2.3.6. Mobility of the Adsorbed Water Molecules
2.3.7. Steps on the (101) Termination
2.3.8. Experimental Studies Devoted to the Interactions of Water Molecules with the (101) Crystal Face
2.4. Reactivity of the Anatase Crystal Terminations with Respect to Water Molecules: The Minority (001), (100), and (110) Terminations
2.4.1. The (001) Surface
2.4.2. The (100) Surface
2.4.3. The (110) Surface
2.4.4. The Trend in the Surface Reactivity
2.5. Investigation of the Anatase Surfaces by Infrared Spectroscopy
2.6. Experimental Investigation of Morphology of the Anatase Nanocrystallites Using XRD, TEM, and FT-IR Techniques
2.7. Calculated Morphology of the Anatase Nanocrystallites
2.7.1. Introductory Remarks
2.7.2. Morphology of Anatase Nanocrystals: ¡°Wulff Constructions¡±
2.7.3. Surface Chemistry and Morphology of Anatase Nanocrystals
2.8. Recent Methods for Investigating and Manipulating the Morphology of Anatase Nanocrystals
2.9. The (110) Crystal Face of Rutile
2.9.1. Introductory Remarks
2.9.2. Surface Structure
2.9.3. Surface Energy
2.9.4. Modes of Adsorption of Water Molecules
2.9.5. Recent Works Devoted to the Modes of Adsorption of Water Molecules
2.9.6. The Structure of the Water Molecules in the ¡°Rutile (110)/Electrolyte Solution Interface¡±
2.10. The (011) Crystal Face of Rutile
2.10.1. Surface Structure, Energy, and Relaxations
2.10.2. Surface Reconstructions
2.10.3. Modes of Adsorption of Water Molecules
2.11. The (100) Crystal Face of Rutile
2.11.1. Surface Structure, Energy, Relaxations, and Reconstructions
2.11.2. Modes of Adsorption of Water Molecules
2.12. The (001) Crystal Face of Rutile
2.12.1. Surface Structure, Energy, Relaxations, and Reconstructions
2.12.2. Modes of Adsorption of Water Molecules
2.13. The (101) Crystal Face of Rutile
2.14. Surface Chemistry and Morphology of the Rutile Nanocrystals
2.15. Charges Localized above the Surface Atoms Exposed by the Anatase and Rutile Surfaces Studied
2.16. Surface Chemistry and Phase Transitions of the Anatase and Rutile Polymorphs
3. Interfacial Chemistry
3.1. A General Description of the Interfacial Region
3.1.1. The Music Model
3.1.2. Basic Stern Model
3.1.3. Triple Layer Model (TLM)
3.1.4. Three Plane Model
3.2. Studies on the Rutile (110) Crystal Termination/Electrolytic Solution Interface: A Bridge between the Surface and Interface Chemistry
3.2.1. Introductory Remarks
3.2.2. Theoretical Calculations
3.2.3. X-ray Studies
3.2.4. Sodium Ions
3.2.5. Calcium Ions
3.2.6. Rubidium Ions
3.2.7. Strontium Ions
3.2.8. Yttrium Ions
3.2.9. Zinc Ions
3.2.10. Cobalt(II) Ions
3.2.11. Chloride and Bromide Ions
3.2.12. Final Remarks
3.3. The Polycrystalline Titanium Oxide/Background Electrolyte Solution Interface
3.3.1. Historical Remarks
3.3.2. Description in Terms of the Music/Basic Stern Model: A Bond Valence Approach
3.3.3. The Influence of Temperature
3.3.4. Investigation of the Subtitle Interface for Anatase of a Nanosized Structure and High Surface Area
3.3.5. Description in Terms of a Multisite/Three Plane Model: An Ab Initio Approach
4. Deposition of Transition Metal Ionic Species on the ¡°Polycrystalline Titanium Oxide/Electrolyte Solution¡± Interface Related to the Synthesis of Supported Catalysts
4.1. Regulation of the Mode of Deposition for a Tailor-Made Synthesis of a Supported Catalyst Based on Titanium Oxide
4.2. Deposition of Transition Metal Ionic Species on the ¡°Polycrystalline Titanium Oxide/Electrolyte Solution¡± Interface Containing Catalytically Active Elements
4.2.1. Introductory Remarks
4.2.2. Co(II) Aqua Complexes
4.2.3. Fe(II) Aqua Complexes
4.2.4. Cu(II) Aqua Complexes
4.2.5. Cr(VI) Oxo-species
4.2.6. Mo(VI) Oxo-species
4.2.7. V(V) Oxo-species
4.2.8. Recent Efforts Based on a Modern Mapping of the Titanium Oxide Protonation/Deprotonation Sites and the Three Plane Model
5. Closing Remarks×îС°Öذõ×ÛÊö¡±ÎÄÕ¡ª¡ª¶þÑõ»¯îѵıíÃæ»¯Ñ§¡¢¹ÌÒº½çÃæ»¯Ñ§¼°ÆäºÏ³É»¯Ñ§
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