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Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

Nature Chemistry volume 10, pages 24–30 (2018)Cite this article

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Abstract

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm–2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

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Figure 1: Electrochemical behaviour of Co-POM/CP electrodes.
Figure 2: Comparative electrochemical behaviour of catalyst/CP electrodes in acidic media, highlighting the superior activity of Co-POM modified electrodes for oxygen evolution.
Figure 3: Stability and benchmarking of catalyst/CP electrodes.

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Acknowledgements

This work was supported by the European Union (project ERC StG, grant CHEMCOMP, no. 279313), the Spanish Ministerio de Economía y Competitividad (MINECO; through projects CTQ2015-71287-R, CTQ2014-52774-P and the Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319), the Generalitat de Catalunya (2014-SGR-797 and 2014SGR-199) and the CERCA Programme/Generalitat de Catalunya. J.M.P. acknowledges the ICREA Foundation for an ICREA Academia award. M.B.A. acknowledges the Generalitat Catalana (AGAUR) for a predoctoral fellowship. The authors also thank Á. Reyes-Carmona for discussions.

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Author notes

  1. Marta Blasco-Ahicart and Joaquín Soriano-López: These authors contributed equally to this work.

Authors and Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, Tarragona, E-43007, Spain

    Marta Blasco-Ahicart, Joaquín Soriano-López & J. R. Galan-Mascaros

  2. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel.lí Domingo 1, Tarragona, E-43007, Spain

    Joaquín Soriano-López, Jorge J. Carbó & Josep M. Poblet

  3. ICREA, Passeig Lluis Companys, 23, Barcelona, E-08010, Spain

    J. R. Galan-Mascaros

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  1. Marta Blasco-Ahicart
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Contributions

J.R.G.-M. proposed the concept. J.R.G.-M., M.B.-A. and J.S.-L. designed the experiments. M.B.-A. and J.S.-L. performed the experiments. All authors participated in data analysis and co-wrote the manuscript.

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Correspondence to J. R. Galan-Mascaros.

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Blasco-Ahicart, M., Soriano-López, J., Carbó, J. et al. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media. Nature Chem 10, 24–30 (2018). https://doi.org/10.1038/nchem.2874

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