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Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst

Nature Chemistry volume 6, pages 362–367 (2014)Cite this article

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Abstract

In any artificial photosynthetic system, the oxidation of water to molecular oxygen provides the electrons needed for the reduction of protons or carbon dioxide to a fuel. Understanding how this four-electron reaction works in detail is important for the development of improved robust catalysts made of Earth-abundant materials, like first-row transition-metal oxides. Here, using time-resolved Fourier-transform infrared spectroscopy and under reaction conditions, we identify intermediates of water oxidation catalysed by an abundant metal-oxide catalyst, cobalt oxide (Co3O4). One intermediate is a surface superoxide (three-electron oxidation intermediate absorbing at 1,013 cm−1), whereas a second observed intermediate is attributed to an oxo Co(IV) site (one-electron oxidation intermediate absorbing at 840 cm−1). The temporal behaviour of the intermediates reveals that they belong to different catalytic sites. Knowledge of the structure and kinetics of surface intermediates will enable the design of improved metal-oxide materials for more efficient water oxidation catalysis.

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Figure 1: Rapid-scan FTIR spectra of water oxidation catalysis.
Figure 2: Electrochemical monitoring of oxygen evolution by photolysis pulse.
Figure 3: Temporal behaviour of superoxide surface intermediate.
Figure 4: Rapid-scan FTIR spectra of water oxidation catalysis.
Figure 5: Temporal behaviour of the 840 cm−1 intermediate assigned to Co(IV)=O.
Figure 6: Proposed photocatalytic mechanism.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical, Geological and Biosciences of the US Department of Energy (contract no. DE-AC02-05CH11231).

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  1. Moreno de Respinis

    Present address: Present address: Delft University of Technology, Department of Chemical Engineering, PO Box 5045, 2600GA Delft, The Netherlands,

Authors and Affiliations

  1. Physical Biosciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, 94720, California

    Miao Zhang, Moreno de Respinis & Heinz Frei

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Contributions

H.F. developed the set-up and designed the experiments. M.Z. and M.D.R. prepared the samples and conducted the rapid-scan FTIR experiments and electrochemical measurements. M.Z. performed the mass spectrometric measurements. H.F. and M.Z. wrote the paper.

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Correspondence to Heinz Frei.

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Zhang, M., de Respinis, M. & Frei, H. Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst. Nature Chem 6, 362–367 (2014). https://doi.org/10.1038/nchem.1874

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