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Chromium segregation in Cr-doped TiO2 (rutile): impact of oxygen activity

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Abstract

This work considers the effect of chromium surface segregation for polycrystalline Cr-doped TiO2 on surface vs. bulk defect disorder. It is shown that annealing of Cr-doped TiO2 (0.04 at% Cr) in the gas phase of variable oxygen activity at 1273 K results in a gradual transition in the valence of chromium at the surface from predominantly Cr3+ species in reduced conditions, p(O2) = 10−12 Pa, to comparable concentrations of both Cr3+ and Cr6+ species in oxidising conditions, p(O2) = 105 Pa. The reported data is considered in terms of defect equilibria leading to the formation of positively and negatively charged chromium in both the cation sub-lattice and interstitial sites. The derived theoretical models represent the effect of oxygen activity on the surface charge and the resulting electric field leading to migration mechanism of charged chromium species.

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Authors and Affiliations

  1. Solar Energy Technologies, Western Sydney University, Penrith, NSW, 2751, Australia

    Kazi A. Rahman, T. Bak & J. Nowotny

  2. School of Chemistry, University of New South Wales, Sydney, NSW, 2052, Australia

    N. Sharma

  3. Centre for Accelerator Science, Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW, 2232, Australia

    A. J. Atanacio

  4. Maryland Energy Innovation Institute, University of Maryland, College Park, MD, 20742, USA

    E. D. Wachsman

  5. School of Science and Health, Western Sydney University, Penrith, NSW, 2751, Australia

    M. Moffitt

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  1. Kazi A. Rahman
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  2. N. Sharma
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Rahman, K.A., Sharma, N., Atanacio, A.J. et al. Chromium segregation in Cr-doped TiO2 (rutile): impact of oxygen activity. Ionics 25, 3363–3372 (2019). https://doi.org/10.1007/s11581-018-2828-4

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