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Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution

Nature Chemistry volume 9, pages 457–465 (2017)Cite this article

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An Erratum to this article was published on 23 January 2018

An Addendum to this article was published on 25 July 2017

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Abstract

Understanding how materials that catalyse the oxygen evolution reaction (OER) function is essential for the development of efficient energy-storage technologies. The traditional understanding of the OER mechanism on metal oxides involves four concerted proton–electron transfer steps on metal-ion centres at their surface and product oxygen molecules derived from water. Here, using in situ18O isotope labelling mass spectrometry, we provide direct experimental evidence that the O2 generated during the OER on some highly active oxides can come from lattice oxygen. The oxides capable of lattice-oxygen oxidation also exhibit pH-dependent OER activity on the reversible hydrogen electrode scale, indicating non-concerted proton–electron transfers in the OER mechanism. Based on our experimental data and density functional theory calculations, we discuss mechanisms that are fundamentally different from the conventional scheme and show that increasing the covalency of metal–oxygen bonds is critical to trigger lattice-oxygen oxidation and enable non-concerted proton–electron transfers during OER.

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Figure 1: Electronic structures of Co-containing perovskite oxides.
Figure 2: Direct evidence of lattice oxygen oxidation involved in the OER of 18O-labelled perovskites.
Figure 3: pH-dependent OER activity on the RHE scale.
Figure 4: OER mechanisms with concerted and non-concerted proton–electron transfer.
Figure 5: Electrochemical oxygen intercalation into brownmillerite SrCoO3−δ followed by the OER.

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Change history

  • 23 June 2017

    In our Article we reported direct experimental evidence for the involvement of lattice oxygen redox chemistry in the perovskite catalysed oxygen evolution reaction (OER). We would like to cite an Article1 that was published prior to ours that readers should be aware of. The Article reports the OER activities of a series of cobaltite perovskites (La1−xSrxCoO3−δ), and its authors rationalize the high activities for materials with x > 0.4 through the participation of lattice oxygen in the OER mechanism, a hypothesis that is supported by density functional theory. References 1. Mefford, J. T. et al. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts. Nat. Commun. 7, 11053 (2016).

  • 21 December 2017

    In the version of this Article originally published, a typographical error meant that the unit on the y-axis label of Fig. 3b incorrectly read 'mA cm-2disk'; it should have read 'mA cm-2oxide'. This has been now corrected in the online versions of the Article.

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Acknowledgements

This work was supported in part by the Skoltech-MIT Center for Electrochemical Energy, the SMART programme, and the Department of Energy (DOE) and National Energy Technology Laboratory (NETL), Solid State Energy Conversion Alliance (SECA) Core Technology Program (Funding Opportunity Number DEFE0009435). This work is also supported in part by the Netherlands Organization for Scientific Research (NWO) within the research programme of BioSolar Cells, co-financed by the Dutch Ministry of Economic Affairs, Agriculture and Innovation. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy (contract no. DE-AC02-05CH11231). The authors would like to acknowledge Dane Morgan and Jean-Marie Tarascon for fruitful discussion.

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Author notes

  1. Alexis Grimaud

    Present address: Present addresses: FRE 3677 ‘Chimie du Solide et Energie’, Collège de France, 75231 Paris Cedex 05, France; Réseau sur le Stockage Electrochimique de l'Energie (RS2E), FR CNRS 3459, 80039 Amiens Cedex, France,

  2. Alexis Grimaud, Oscar Diaz-Morales and Binghong Han: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Alexis Grimaud, Yueh-Lin Lee & Yang Shao-Horn

  2. Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA, Leiden, The Netherlands

    Oscar Diaz-Morales & Marc T. M. Koper

  3. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Binghong Han, Wesley T. Hong, Kelsey A. Stoerzinger & Yang Shao-Horn

  4. Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Yueh-Lin Lee, Livia Giordano & Yang Shao-Horn

  5. Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, Milano, Italy

    Livia Giordano

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Contributions

Y.S.-H. and A.G. designed the experiments. A.G. and W.T.H. carried out the synthesis, structural and chemical analysis. A.G. and B.H. performed the electrochemical measurements. O.D.-M. and M.T.M.K. conducted the OLEMS measurements. Y.-L.L and L.G. carried out the DFT calculations. Y.S.-H. wrote the manuscript and all authors edited the manuscript.

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Correspondence to Yang Shao-Horn.

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Grimaud, A., Diaz-Morales, O., Han, B. et al. Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nature Chem 9, 457–465 (2017). https://doi.org/10.1038/nchem.2695

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