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WATER OXIDATION

Heterogeneous electrocatalysis goes chemical

Nature Catalysis volume 4, pages 4–5 (2021)Cite this article

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Despite over a century of research to understand heterogeneous electrocatalysis, the precise mechanisms of action remain poorly understood. Now, it is proposed that the oxygen evolution reaction on IrOx is driven by changes in the redox state of the Ir–O active sites, rather than by changes in the interfacial electric field.

Electrocatalysis is essential for the efficient interconversion of electrical and chemical energy. Elementary and multi-step electrocatalytic electron-transfer (ET) reactions at electrode surfaces are typically classified as either inner- or outer-sphere. In outer-sphere heterogeneous processes, the electrons transfer by tunnelling between the electrode and redox-active species through a solvent layer. The kinetics of interfacial outer-sphere ET are well described by Marcus theory where the ET rate increases exponentially with the thermodynamic driving force (that is, applied overpotential) until the driving force approaches the reorganizational energy, beyond which the rate becomes insensitive to further increases in overpotential. Since outer-sphere processes involve no direct chemical interaction between the redox species and the electrode surface, outer-sphere reactions are typically insensitive to the chemical composition and surface structure of the electrode.

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Fig. 1: Heterogeneous water oxidation via surface chemical reactions.

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Authors and Affiliations

  1. The Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, OR, USA

    Shannon W. Boettcher

  2. The Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Yogesh Surendranath

  3. Center for Interfacial Ionics, Eugene, OR, USA

    Shannon W. Boettcher & Yogesh Surendranath

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  1. Shannon W. Boettcher
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  2. Yogesh Surendranath
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Correspondence to Shannon W. Boettcher or Yogesh Surendranath.

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Boettcher, S.W., Surendranath, Y. Heterogeneous electrocatalysis goes chemical. Nat Catal 4, 4–5 (2021). https://doi.org/10.1038/s41929-020-00570-1

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