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The kinetics of metal oxide photoanodes from charge generation to catalysis

Nature Reviews Materials volume 6, pages 1136–1155 (2021)Cite this article

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Abstract

Generating charge carriers with lifetimes long enough to drive catalysis is a critical aspect for photoelectrochemical and photocatalytic systems, and a key determinant of their efficiency. Metal oxides are widely explored as photoanodes for photoelectrochemical water oxidation. However, their application is limited by the disparity between the picosecond–nanosecond lifetimes of electrons and holes photoexcited in bulk metal oxides versus the millisecond–second timescale of water oxidation catalysis. This Review addresses the charge-carrier dynamics underlying the performance of metal oxide photoanodes and their ability to drive photoelectrochemical water oxidation, alongside comparison with metal oxide function in photocatalytic and electrocatalytic systems. We assess the dominant kinetic processes determining photoanode performance, namely, charge generation, polaron formation and charge trapping, bulk and surface recombination, charge separation and extraction, and, finally, the kinetics of water oxidation catalysis. We examine approaches to enhance performance, including material selection, doping, nanostructuring, junction formation and/or co-catalyst deposition. Crucially, we examine how such performance enhancements can be understood from analyses of carrier dynamics and propose design guidelines for further material or device optimization.

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Fig. 1: Timescales of charge-carrier dynamics in metal oxide photoanodes.
Fig. 2: Carrier movement in the bulk.
Fig. 3: Carrier movement at the surface.
Fig. 4: Solid-state junctions.
Fig. 5: Kinetic models for water oxidation catalysis.

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Acknowledgements

The authors acknowledge financial support from the European Research Council (project Intersolar 291482) and the European Union’s Horizon 2020 research and innovation programme under grant agreement 732840-A-LEAF. L.S. acknowledges her Marie Skłodowska-Curie fellowship funding (H2020-MSCA-IF-2016, grant no. 749231). The authors further acknowledge the UKRI Strategic Priorities Fund for funding, thank C. A. Mesa, M. Sachs, B. Moss and S. Selim for their thoughts and suggestions, and thank M. Sachs for compiling, and providing some of, the data in Fig. 2b.

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  1. Department of Chemistry and Centre for Processable Electronics, Imperial College London, London, UK

    Sacha Corby, Reshma R. Rao, Ludmilla Steier & James R. Durrant

  2. Department of Materials, Imperial College London, London, UK

    Ludmilla Steier

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S.C. led the drafting of the manuscript, with R.R.R. leading the sections on water oxidation catalysis. All authors contributed to editing the manuscript prior to submission.

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Corby, S., Rao, R.R., Steier, L. et al. The kinetics of metal oxide photoanodes from charge generation to catalysis. Nat Rev Mater 6, 1136–1155 (2021). https://doi.org/10.1038/s41578-021-00343-7

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