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Local ordering and electronic signatures of submonolayer water on anatase TiO2(101)

Nature Materials volume 8, pages 585–589 (2009)Cite this article

Abstract

The interaction of water with metal oxide surfaces is of fundamental importance to various fields of science, ranging from geophysics to catalysis and biochemistry1,2,3,4. In particular, the discovery that TiO2 photocatalyses the dissociation of water5 has triggered broad interest and intensive studies of water adsorption on TiO2 over decades6. So far, these studies have mostly focused on the (110) surface of the most stable polymorph of TiO2, rutile, whereas it is the metastable anatase form that is generally considered photocatalytically more efficient. The present combined experimental (scanning tunnelling microscopy) and theoretical (density functional theory and first-principles molecular dynamics) study gives atomic-scale insights into the adsorption of water on anatase (101), the most frequently exposed surface of this TiO2 polymorph. Water adsorbs as an intact monomer with a computed binding energy of 730 meV. The charge rearrangement at the molecule–anatase interface affects the adsorption of further water molecules, resulting in short-range repulsive and attractive interactions along the [010] and directions, respectively, and a locally ordered (2×2) superstructure of molecular water.

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Figure 1: The TiO2 anatase (101) surface.
Figure 2: Hopping and short-range ordering of water on anatase (101).
Figure 3: Ordered water overlayer on anatase (101).
Figure 4: Theoretical results for an adsorbed water monomer on anatase (101).
Figure 5: Calculated adsorption configurations of water on anatase (101).

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Acknowledgements

This work was supported by DoE award DE-FG02-05ER15702. We thank C. Di Valentin for participating in the early stages of this project and H. Cheng for the constant density STM program. A.T. thanks the UK’s Royal Society for financial support.

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Author notes

  1. Yunbin He

    Present address: Present address: Faculty of Materials Sciences and Engineering, Hubei University, No. 11 Xueyuan Road, Wuchang, Wuhan 430062, China,

Authors and Affiliations

  1. Department of Physics, Tulane University, New Orleans, Louisiana 70118, USA

    Yunbin He, Olga Dulub & Ulrike Diebold

  2. Department of Chemistry and Materials Simulation Laboratory, University College London, London WC1H 0AJ, UK

    Antonio Tilocca

  3. Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA

    Annabella Selloni

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  1. Yunbin He
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  2. Antonio Tilocca
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  4. Annabella Selloni
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  5. Ulrike Diebold
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Correspondence to Yunbin He or Ulrike Diebold.

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He, Y., Tilocca, A., Dulub, O. et al. Local ordering and electronic signatures of submonolayer water on anatase TiO2(101). Nature Mater 8, 585–589 (2009). https://doi.org/10.1038/nmat2466

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