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Activation of Water in Titanium Dioxide Photocatalysis by Formation of Surface Hydrogen Bonds: An In Situ IR Spectroscopy Study
Abstract
The hole‐driving oxidation of titanium‐coordinated water molecules on the surface of TiO 2 is both thermodynamically and kinetically unfavorable. By avoiding the direct coordinative adsorption of water molecules to the surface Ti sites, the water can be activated to realize its oxidation. When TiO 2 surface is covered by the H‐bonding acceptor F, the first‐layer water adsorption mode is switched from Ti coordination to a dual H‐bonding adsorption on adjacent surface F sites. Detailed in situ IR spectroscopy and isotope‐labeling studies reveal that the adsorbed water molecules by dual H‐bonding can be oxidized to O 2 even in the absence of any electron scavengers. Combined with theoretical calculations, it is proposed that the formation of the dual H‐bonding structure can not only enable the hole transfer to the water molecules thermodynamically, but also facilitate kinetically the cleavage of OH bonds by proton‐coupled electron transfer process during water oxidation.
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Cites
Progress, challenge and perspective of heterogeneous photocatalysts
Qu, Y., & Duan, X. (2013) · Chem. Soc. Rev. · doi:10.1039/c2cs35355e · Cited by 1,466
Cited by
Oxygen Vacancy‐Mediated Photocatalysis of BiOCl: Reactivity, Selectivity, and Perspectives
Li, H., Li, J., Ai, Z., Jia, F., & Zhang, L. (2018) · Angewandte Chemie International Edition · doi:10.1002/anie.201705628 · Cited by 1,207
Wang, W., Deng, C., Xie, S., Li, Y., Zhang, W., Sheng, H., Chen, C., & Zhao, J. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c00206 · Cited by 523
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Metadata
- Authors
- Sheng, H., Zhang, H., Song, W., Ji, H., Ma, W., Chen, C., & Zhao, J.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2015-03-25
- Volume
- 54
- Issue
- 20
- Pages
- 5905-5909
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2144782788
- Cited by
- 187
- References
- 1
- FWCI
- 3.62
- Type
- journal article
- Language
- en
- Open access
- closed
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- Sheng, H., Zhang, H., Song, W., Ji, H., Ma, W., Chen, C., & Zhao, J. (2015). Activation of Water in Titanium Dioxide Photocatalysis by Formation of Surface Hydrogen Bonds: An In Situ IR Spectroscopy Study. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.201412035
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