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The mechanism of oxygen evolution at superactivated gold electrodes in aqueous alkaline solution

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Abstract

The cathodic superactivation of gold using a repetitive potential cycling procedure is reported, and its significance for the oxygen evolution reaction is discussed. The superactivated surfaces exhibit a transient oxygen evolution response subsequent to monolayer oxidation and prior to extensive visible oxygen evolution. The kinetics of this oxygen evolution process are studied using a variety of transient and steady-state electrochemical techniques. The Tafel slope is shown to decrease with increased activation of the gold surface from ca. 120 to ca. 48 mV dec−1, and the charge transfer kinetics are enhanced by over three orders of magnitude for the superactivated electrodes. A mechanistic scheme involving the formation of monomeric Au(III) hydroxyl complexes of the form Au(OH)6 3− is proposed. The latter are of a transient nature and may be regarded as intermediates in the early stages of hydrous ß-oxide growth. These labile species may catalyse oxygen evolution by enhancing the formation of peroxy species that subsequently decompose with loss of oxygen gas from the surface oxide. This novel mechanistic route is in excellent agreement with recent literature studies and has the potential to unite a number of strands in the current understanding of the oxygen evolution reaction at gold surfaces.

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Notes

  1. For a single electron transfer process, the transfer coefficient α can be equated with the symmetry factor β which, in the case of a symmetrical potential energy barrier, is equal to 0.5. For a multi-electron transfer process, the situation is more complicated and α is related to β as follows: \( {a}_f=\frac{n_f}{v}+{n}_r\beta \), where the subscript f denotes the forward reaction, n f is the number of electrons transferred before the rate-determining step (rds), v is the number of occurrences of the rds in the electrode reaction and n r is the number if electrons involved in the rds. However, in terms of a mechanistic analysis, it is useful to view a multistep electrode process as a sequence of one-electron transfer steps and/or chemical steps. Hence, β can be applied to the treatment of each elementary electron transfer step. In practical terms, it should be noted that the experimentally measurable quantity—the Tafel slope b—is related to α as follows: \( b=2.303\left(\frac{RT}{aF}\right) \) [70–74].

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Acknowledgements

This paper is dedicated to Prof. Stephen Fletcher on the occasion of his 65th birthday. He has truly been an inspiration to physical electrochemists for many years. This publication has emanated in part from research conducted with the financial support of Science Foundation Ireland (SFI) under grant number SFI/10/IN.1/I2969.

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  1. Trinity Electrochemical Energy Conversion and Electrocatalysis (TEECE) Group, School of Chemistry and CRANN, Trinity College, Dublin 2, Ireland

    Richard L. Doyle & Michael E. G. Lyons

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Correspondence to Richard L. Doyle.

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Doyle, R.L., Lyons, M.E.G. The mechanism of oxygen evolution at superactivated gold electrodes in aqueous alkaline solution. J Solid State Electrochem 18, 3271–3286 (2014). https://doi.org/10.1007/s10008-014-2665-y

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  • DOI: https://doi.org/10.1007/s10008-014-2665-y

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