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Energetics and kinetics of light-driven oxygen evolution at semiconductor electrodes: the example of hematite

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Abstract

Light-driven water-splitting (photoelectrolysis) at semiconductor electrodes continues to excite interest as a potential route to produce hydrogen as a sustainable fuel, but surprisingly little is known about the kinetics and mechanisms of the reactions involved. Here, some basic principles of semiconductor photoelectrochemistry are reviewed with particular emphasis on the effects of slow interfacial electron transfer at n-type semiconductors in the case of light-driven oxygen evolution. A simple kinetic model is outlined that considers the competition between interfacial transfer of photogenerated holes and surface recombination. The model shows that, if interfacial charge transfer is very slow, the build-up of holes at the surface will lead to substantial changes in the potential drop across the Helmholtz layer, leading to non-ideal behavior (Fermi level pinning). The kinetic model is also used to predict the response of photoanodes to chopped illumination and to periodic perturbations of illumination and potential. Recent experimental results obtained for α-Fe2O3 (hematite) photoanodes are reviewed and interpreted within the framework of the model.

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Acknowledgments

The author thanks Dr. Upul Wijayantha and members of his research group for their collaborative work on hematite electrodes.

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Authors and Affiliations

  1. Department of Chemistry, University of Bath, Bath, BA2 7AY, UK

    Laurence M. Peter

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  1. Laurence M. Peter
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Correspondence to Laurence M. Peter.

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Dedicated to Professor Alexander Milchev on the occasion of his 70th birthday.

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Peter, L.M. Energetics and kinetics of light-driven oxygen evolution at semiconductor electrodes: the example of hematite. J Solid State Electrochem 17, 315–326 (2013). https://doi.org/10.1007/s10008-012-1957-3

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  • DOI: https://doi.org/10.1007/s10008-012-1957-3

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