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  Probing the formation and optical properties of Ti3+–TiO2 with (001) exposed crystal facet by ethanol-assisted fluorination

Wang, J., Lin, W., Zhou, S., Li, Z., Hu, H., Tao, Y., et al. (2021). Probing the formation and optical properties of Ti3+–TiO2 with (001) exposed crystal facet by ethanol-assisted fluorination. New Journal of Chemistry, 45(28), 12453-12463. doi:10.1039/D1NJ01591E.

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 Creators:
Wang, Jian1, Author
Lin, Wei1, Author
Zhou, Shulan2, Author
Li, Z.3, Author              
Hu, Hao1, Author
Tao, Yinglong1, Author
Zhou, Shijian1, Author
Zhaod, Xian4, Author
Kong, Yan1, Author
Affiliations:
1State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, ou_persistent22              
2Department of Material Science and Engineering, Jingdezhen Ceramic Institute, ou_persistent22              
3Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
4State Key Laboratory of Crystal Material, Institute of Crystal Material, Shandong University, ou_persistent22              

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 Abstract: In TiO2 based photocatalysis, it is crucial to conceal the catalytically active Ti3+ defect sites inside the crystal, since the Ti3+ defects on the surface can be rapidly lost after capturing O2 molecules in the air. In this work, we report a novel method to synthesize TiO2 with Ti3+ defects that are exclusively embedded in the bulk lattice near the surface. We show that the binary synthetic system consisting of ethanol and HF is indispensable for the precise location control of the formed Ti3+ defects, and the near-surface bulk Ti3+ defects can only be formed under the coexistence of both these reagents. The underlying mechanism of achieving such remarkable control of the position of the Ti3+ defect sites was clarified by extensive analysis through X-ray diffraction, electron microscopy, electron spin resonance, X-ray photoelectron spectroscopy, as well as theoretical simulation using the DFT+U method. We show that ethanol plays a crucial role in assisting fluorine atoms adsorbing on the exposed (001) crystal facets, penetrating the near-surface bulk lattice and inducing Ti3+ defect formation via substitution of oxygen atoms.

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Language(s): eng - English
 Dates: 2021-04-012021-06-082021-06-092021-07-28
 Publication Status: Published in print
 Pages: 11
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D1NJ01591E
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Title: New Journal of Chemistry
  Abbreviation : New J. Chem.
Source Genre: Journal
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Publ. Info: London : Royal Society of Chemistry
Pages: - Volume / Issue: 45 (28) Sequence Number: - Start / End Page: 12453 - 12463 Identifier: ISSN: 1144-0546
CoNE: https://pure.mpg.de/cone/journals/resource/954928578776