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DFT model cluster studies of O2 adsorption on hydrogenated titania sub-nanoparticles

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Abstract

In the present paper, we examine the general applicability of different TiO2 model clusters to study of local chemical events on TiO2 sub-nanoparticles. Our previous DFT study of TiO2 activation through H adsorption and following deactivation by O2 adsorption using small amorphous Ti8O16 cluster were complemented by examination of rutile-type and spherical Ti15O30 nanoclusters. The obtained results were thoroughly compared with experimental data and results of related computational studies using other TiO2 models including periodic structures. It turned out that all considered model TiO2 model systems provide qualitatively similar results. It was shown that atomic hydrogen is adsorbed with negligible activation energy on surface O atoms, which is accompanied by the appearance of reduced Ti3+ species and corresponding localized band gap 3d-Ti states. Oxygen molecule is adsorbed on Ti3+ sites spontaneously forming molecular O2 – species by capturing an extra electron of Ti3+ ion, which results in disappearance of Ti3+ species and corresponding band gap states. Calculated g-tensor values of Ti3+ and O2 – species agree well with the results of EPR studies and do not depend on the used TiO2 model cluster. Additionally, it was shown that the various cluster calculations provide results comparable with the calculations of periodic structures with respect to the modeling of chemical processes under study. As a whole, the present study approves the validity of molecular cluster approach to study of local chemical events on TiO2 sub-nanoparticles.

Electronic structure diagrams for small Ti8O16H and large Ti15O30H hydrogenated clusters

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Acknowledgments

The authors thank Prof. Alexei Emeline and Prof. Vladimir Ryabchuk for fruitful discussions. The present work was supported by Russian Foundation of Basic Research (Grant 10-03-00638-а) and St. Petersburg State University (Grant 11.37.25.2011). Computational resources were provided by Service of Informational Technologies of St. Petersburg State University (St. Petersburg, Russia).

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  1. V. A. Fock Institute of Physics, St. Petersburg State University, Ulyanovskaya Str. 1, St. Petersburg, 198504, Russia

    Alexey S. Andreev, Vyacheslav N. Kuznetsov & Yuri V. Chizhov

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  1. Alexey S. Andreev
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  2. Vyacheslav N. Kuznetsov
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  3. Yuri V. Chizhov
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Correspondence to Yuri V. Chizhov.

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Andreev, A.S., Kuznetsov, V.N. & Chizhov, Y.V. DFT model cluster studies of O2 adsorption on hydrogenated titania sub-nanoparticles. J Mol Model 19, 5063–5073 (2013). https://doi.org/10.1007/s00894-013-2000-z

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