Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C

Abstract

Electrochemical water splitting in acidic conditions offers important advantages over that in alkaline systems, but the technological progress is limited by the lack of inexpensive and efficient anode catalysts that can stably operate at a low pH and elevated temperature. Here we demonstrate oxygen evolution catalysts that are based on non-noble metals, are formed in situ during electrooxidation of acidic water and exhibit a high stability in operation due to a self-healing mechanism. The highly disordered mixed metal oxides generated from dissolved cobalt, lead and iron precursors sustain high water oxidation rates at reasonable overpotentials. Moreover, utilizing a sufficiently robust electrode substrate allows for a continuous water oxidation at temperatures up to 80 °C and rates up to 500 mA cm−2 at overpotentials below 0.7 V with an essentially flat support and with no loss in activity. This robust operation of the catalysts is provided by the thermodynamically stable lead oxide matrix that accommodates homogeneously distributed catalytic dopants.

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Fig. 1: Cyclic voltammetric (scan rate 0.020 V s−1) oxidation of aqueous H2SO4 that contains Co2+ (5 mM), Fe3+ (1 mM) and Pb2+ (0.5 mM).
Fig. 2: Potentiostatic oxidation of aqueous H2SO4 that contains Co2+ (5 mM), Fe3+ (1 mM) and Pb2+ (0.5 mM) under different conditions.
Fig. 3: Microscopic analysis of the CoFePbOx catalysts deposited on FTO.
Fig. 4: Characterization of CoFePbOx.

Data availability

The data that support all findings of this study are available from the corresponding author upon request.

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Acknowledgements

The authors thank B.H.R. Suryanto (Monash University) for the instrumental support throughout the study, and P. Kappen and C. Glover (Australian Synchrotron) for support in the XAS experiments. The authors acknowledge the use of facilities within the Monash Centre for Electron Microscopy (funded by the Australian Research Council grant LE110100223) and Monash X-ray Platform (funded by Australian Research Council grant LE130100072). Part of this research was undertaken on the XAS beamline at the Australian Synchrotron, part of ANSTO. Funding of this work by the Australian Research Council through the ARC Centre of Excellence for Electromaterials Science (CE140100012) and by the Australian Renewable Energy Agency (ARENA contract no. 2018/RND008) is appreciated.

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M.C. designed and undertook electrochemical experiments, performed the SEM/EDX and XRD analysis, analysed and interpreted data, and co-wrote the paper. J.G. undertook electrochemical experiments, analysed and interpreted data, and co-wrote the paper. M.F. undertook O2 detection and ICP-OES analysis, and contributed to data analysis. B.J. undertook XAS experiments. T.W. collected and analysed TEM data. T.R.G. collected and analysed XPS data. N.P. undertook cross-sectional SEM and ICP-OES analyses. C.N. undertook SEM analysis and assisted with data analysis. D.R.M. interpreted data and contributed to the manuscript preparation. R.K.H. collected and analysed XAS data, interpreted data and contributed to the manuscript preparation. A.N.S. conceived and directed the project, designed experiments, analysed and interpreted data, and co-wrote the paper.

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Correspondence to Alexandr N. Simonov.

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Supplementary Information

Supplementary Figures 1–29, Supplementary Tables 1–6 and Supplementary References.

Supplementary Video

In situ generation and operation of the CoFePbOx water oxidation catalyst in 0.1 M H2SO4 at 23 °C.

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Chatti, M., Gardiner, J.L., Fournier, M. et al. Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C. Nat Catal 2, 457–465 (2019). https://doi.org/10.1038/s41929-019-0277-8

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