Comparison of the electronic structure of anatase and rutile TiO2 single-crystal surfaces using resonant photoemission and x-ray absorption spectroscopy

A. G. Thomas, W. R. Flavell, A. K. Mallick, A. R. Kumarasinghe, D. Tsoutsou, N. Khan, C. Chatwin, S. Rayner, G. C. Smith, R. L. Stockbauer, S. Warren, T. K. Johal, S. Patel, D. Holland, A. Taleb, and F. Wiame
Phys. Rev. B 75, 035105 – Published 5 January 2007

Abstract

A comparison of the electronic structure of rutile (110), anatase (101), and anatase (001) single-crystal surfaces has been made using resonant photoemission and x-ray absorption spectroscopy. Under identical preparative conditions, the anatase (101) surface shows the lowest Ti3d and 4sp hybridization in the states close to the valence-band maximum of the three surfaces. It also shows the highest concentration of surface-oxygen vacancies. The effect on the electronic structure of modifying the surface preparative route and thus the concentration of surface-oxygen vacancies is examined. The σ-antibonding Ti3degO2p hybridization (probed by XAS) is reduced by the removal of surface-oxygen. Photoemission shows that as the number of surface-defects is increased, the O2pTi3dt2gπ-bonding interaction is disrupted. For the anatase (101) surface it is found that as the number of surface-oxygen vacancies is increased, the Ti3d and 4sp contributions at the valence-band maximum are reduced. We discuss the correlation between electronic structure and photocatalytic activity of the different polymorphs of TiO2.

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  • Received 17 July 2006

DOI:https://doi.org/10.1103/PhysRevB.75.035105

©2007 American Physical Society

Authors & Affiliations

A. G. Thomas*, W. R. Flavell, A. K. Mallick, A. R. Kumarasinghe, D. Tsoutsou, N. Khan, C. Chatwin, S. Rayner, and G. C. Smith

  • School of Physics and Astronomy, University of Manchester, Sackville Street Building, P.O. Box 88, Manchester M60 1QD, United Kingdom

R. L. Stockbauer

  • Louisiana State University, Baton Rouge, Louisiana 70803, USA

S. Warren

  • ESRF, Polygone Scientifique Louis Néel, 6, rue Jules Horowitz, 38000 Grenoble, France

T. K. Johal, S. Patel, and D. Holland

  • CCLRC, Daresbury Laboratory, Warrington, Cheshire WA5 4AD, United Kingdom

A. Taleb and F. Wiame§

  • LURE, Universitaire Paris-Sud, Boîte Postale 34-91898 Orsay, France

  • *Corresponding author. Electronic address: a.g.thomas@manchester.ac.uk
  • Present address: CCLC Nantes Atlantique, Centre René Gauducheau, Blvd. Prof. Jacques Monod, 44805 St. Herblain, France.
  • Present address: Synchrotron Soleil, L’Orme des Merisiers, Saint Aubin-BP 48, 91192 Gif sur Yvette, France.
  • §Present address: Laboratoire de Physico-Chimie des Surfaces, UMR 7045 ENSCP-CNRS, 11 rue Pierre et Marie Curie, F-75005 Paris, France.

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Issue

Vol. 75, Iss. 3 — 15 January 2007

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