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A soluble copper–bipyridine water-oxidation electrocatalyst

Nature Chemistry volume 4, pages 498–502 (2012)Cite this article

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Abstract

The oxidation of water to O2 is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for this reaction, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Reported here is the first copper-based catalyst for electrolytic water oxidation. Copper–bipyridine–hydroxo complexes rapidly form in situ from simple commercially available copper salts and bipyridine at high pH. Cyclic voltammetry of these solutions at pH 11.8–13.3 shows large, irreversible currents, indicative of catalysis. The production of O2 is demonstrated both electrochemically and with a fluorescence probe. Catalysis occurs at about 750 mV overpotential. Electrochemical, electron paramagnetic resonance and other studies indicate that the catalyst is a soluble molecular species, that the dominant species in the catalytically active solutions is (2,2′-bipyridine)Cu(OH)2 and that this is among the most rapid homogeneous water-oxidation catalysts, with a turnover frequency of ~100 s−1.

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Figure 1: CVs of solutions containing 1.0 mM total Cu and bpy.
Figure 2: Evolution of O2 during bulk electrolysis.
Figure 3: The aqueous speciation of a 1:1 copper(II):bpy solution, observed by EPR.
Figure 4: Voltammograms of 100 µM bpy/Cu2+ solutions showing the variation in catalytic current with pH.
Figure 5: Dependence of the catalytic current on copper concentration.

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Acknowledgements

We thank the US National Science Foundation Center for Enabling New Technologies Through Catalysis for support. We are grateful to C. Waidmann for his studies of the oxidation of dimeric copper complexes50 that laid critical groundwork for the work reported here, and to W.B. Tolman for discussions.

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  1. Department of Chemistry, University of Washington, Seattle, Washington, 98195, USA

    Shoshanna M. Barnett, Karen I. Goldberg & James M. Mayer

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Contributions

S.M.B. and J.M.M. conceived and designed the experiments, S.M.B. performed all the experiments, S.M.B., K.I.G. and J.M.M. analysed the data and co-wrote the paper.

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Correspondence to James M. Mayer.

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Barnett, S., Goldberg, K. & Mayer, J. A soluble copper–bipyridine water-oxidation electrocatalyst. Nature Chem 4, 498–502 (2012). https://doi.org/10.1038/nchem.1350

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