Hybrid exchange density functional study of vicinal anatase TiO2 surfaces

F. F. Sanches, G. Mallia, L. Liborio, U. Diebold, N. M. Harrison

Thomas Young Centre, Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom
Institut für Angewandte Physik, Technische Universität Wien, 1040 Wien, Austria
STFC, Daresbury Laboratory, Daresbury, Warrington WA4 4AD, United Kingdom

Phys. Rev. B 89 (2014) 245309

The observation of photocatalytic water splitting on the surface of anatase TiO2 crystals has stimulated many investigations of the underlying processes. Nevertheless, a molecular-level understanding of the reaction is not available. This requires knowledge of the crystal facets present, the atomistic structure of the surfaces, and thus the reaction sites involved. In this paper we establish the atomistic structure of two surfaces, vicinal to the low-energy (101) surface. We compute the relative stability and electronic properties of the (514) and (516) surfaces and compare these to the low-index (101), (001), and (100) surfaces. The (516) surface is remarkably stable, and is predicted to contribute significantly to the surface area of a crystallite in equilibrium. We simulate constant current scanning tunneling microscopy images and, by comparing with those measured, we conclude that a surface previously observed in a miscut single crystal is the (516) surface described here. The computed stability of this surface indicates that it will be present in TiO2 nanostructures and the relative positions of its band edges suggests that it will play a significant role in the water-TiO2 reactions in solar water splitting.

Reprints available from Ulrike Diebold (diebold at iap_tuwien_ac_at).

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