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DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption

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Abstract

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H2O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO2 surface.

The chemisorption of benzyl alcohol on TiO2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light

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Acknowledgements

The support of the National Natural Science Foundation of China (21273081) is greatly appreciated. Financial support from the Project supported by Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2011) is also acknowledged.

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Authors and Affiliations

  1. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University, Guangzhou, 510006, China

    Lei Zhao & Feng Long Gu

  2. Department of Chemistry and Biochemistry, California State University Northridge, Northridge, CA, 91330, USA

    Lei Zhao, Minjae Kim & Maosheng Miao

  3. Department of Physics and Materials Science, City University of Hong Kong, Hong Kong, SAR, China

    Rui-Qin Zhang

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  1. Lei Zhao
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Correspondence to Feng Long Gu.

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Zhao, L., Gu, F.L., Kim, M. et al. DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption. J Mol Model 23, 285 (2017). https://doi.org/10.1007/s00894-017-3451-4

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