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The electrochemistry of gold: II the electrocatalytic behaviour of the metal in aqueous media

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Abstract

Chemistry Department, University College Cork, Ireland Although it is the noblest and most inert of metals, and is a very weak chemisorber, gold displays a very wide range of electrocatalytic activity — especially in base. Such unexpected behaviour is rationalized here in terms of the unusual properties of nanocluster, microparticles or quantum dots. Such species, present as defects at the metal surface, undergo oxidation at unusually low potentials (significantly lower than that of bulk gold) in a process known as premonolayer oxidation. The resulting low coverage (or incipient) oxide species are assumed to be the mediators for oxidation reactions while unoxidized active gold atoms, present at lower potentials, often act as the mediators for reduction. Electrocatalysis on noble metals is quite often confined to the double layer region and only low coverage metal atoms at active sites are involved. The enhanced activity of gold in base is readily rationalized in terms of a super-Nernstian E/pH effect. The unusual properties of metal nanoclusters may also be used to rationalize the surprisingly high level of catalytic activity of oxide-supported gold microparticles as reported recently by Haruta and co-workers.

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  1. Chemistry Department, University College Cork, Ireland

    L D Burke & P F Nugent

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  1. L D Burke
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  2. P F Nugent
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Lawrence Declan Burke received his BSc and MSc from University College Cork in 1959 and 1961, respectively, and a PhD in 1964 from Queen’s University Belfast where he worked with FA Lewis on the palladium hydride system. He spent a year as an Alexander von Humbolt Fellow in Karlsruhe University, Germany, where he worked on solid state electrochemistry with Professor Hans Rickert. Since returning to Cork he has been involved in an extensive investigation of the electrochemistry of metals, oxides and especially hydrous oxides. This work, which is concerned largely with the unusual or non-ideal behaviour of these systems, is relevant to such areas as electrocatalysis, electrochromic systems, electroless deposition of metals, etc. Professor Burke was awarded Fellowship of the Electrochemical Society in 1995.

Patrick Francis Nugent successfully completed his PhD degree on research into the electrochemistry of gold in aqueous media in May 1998.

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Burke, L.D., Nugent, P.F. The electrochemistry of gold: II the electrocatalytic behaviour of the metal in aqueous media. Gold Bull 31, 39–50 (1998). https://doi.org/10.1007/BF03214760

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