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Toward sustainable energy: photocatalysis of Cr-doped TiO2: 2. effect of defect disorder

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Abstract

The present chain of five papers considers the concept of solar-to-chemical energy conversion using TiO2-based semiconductors. The series reports the effect of chromium on the key performance-related properties of polycrystalline TiO2 (rutile), including electronic structure, photocatalytic activity, intrinsic defect disorder, electrochemical coupling and surface versus bulk properties. In this work, we show that the effect of chromium on photocatalytic performance of TiO2 depends on its elemental content and the related defect disorder that is determined by oxygen activity in the oxide lattice. At high oxygen activity, chromium leads to enhanced photocatalytic performance only for dilute solid solutions (up to 0.04–0.043 at.% Cr). Higher chromium content results in a decrease of photocatalytic activity below that for pure TiO2, despite the observed substantial decrease of the band gap. The photocatalytic performance of Cr-doped TiO2 annealed in reducing conditions is low within the entire studied range of compositions. The obtained results led to derivation of a theoretical model representing the mechanism of the light-induced reactivity of TiO2 with water and the related charge transfer. The photocatalytic performance is considered in terms of a competitive effect of several key performance-related properties. The performance is predominantly influenced by the concentration of titanium vacancies acting as reactive surface sites related to anodic charge transfer.

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Notes

  1. The species in the solid phase are represented according to the Kroger-Vink notation [39]

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Authors and Affiliations

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

    Kazi Akikur Rahman, Tadeusz Bak & Janusz Nowotny

  2. Australian Nuclear Science and Technology Organisation, Kirrawee, NSW, 2232, Australia

    Armand Atanacio & Mihail Ionescu

Authors
  1. Kazi Akikur Rahman
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  2. Tadeusz Bak
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  3. Armand Atanacio
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  4. Mihail Ionescu
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  5. Janusz Nowotny
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Corresponding author

Correspondence to Janusz Nowotny.

Additional information

New insight

1. Reduction of the band gap has little effect on photocatalytic performance of Cr-doped TiO2.

2. The photocatalytic activity of Cr-doped TiO2 formed in oxidising conditions changes with composition. The photocatalytic performance increases within dilute solid solutions, up to 0.04 at.%, and decreases at higher chromium content.

3. The effect of chromium on photocatalytic activity may be considered in terms of a competitive effect of the key performance-related properties.

Highlights

1. The incorporation of chromium into the TiO2 lattice results in an increase of photocatalytic activity only for dilute solid solutions (up to 0.04 at% Cr) annealed in oxidising conditions.

2. Chromium results in a decrease of photocatalytic activity when annealed in reducing conditions.

3. Photocatalytic activity of Cr-TiO2 depends on several defect-related properties that have competitive effect on performance.

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Rahman, K.A., Bak, T., Atanacio, A. et al. Toward sustainable energy: photocatalysis of Cr-doped TiO2: 2. effect of defect disorder. Ionics 24, 327–341 (2018). https://doi.org/10.1007/s11581-017-2370-9

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  • DOI: https://doi.org/10.1007/s11581-017-2370-9

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