Elsevier, Current Opinion in Electrochemistry, 1(1), p. 7-15, 2017
DOI: 10.1016/j.coelec.2016.12.004
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Gold surfaces are widely used in electrochemistry whilst gold nanoparticles have very many uses, with both the surfaces and the particles often being protected by sulfur-bound organic ligands. The ligands not only provide chemical stability but also directly participate in many desired processes. This review considers the diversity of known atomic structures for gold-sulfur interfaces, how these structures facilitate a diversity of mechanisms in electrochemical applications, and why this is possible based on recent advances in the basic understanding of the electronic structure of gold-sulfur bonds. Believed once to be Au(I)-thiolate in character and hence distinctly different to physisorbed thiols and disulfides, chemisorbed bonds are shown to be Au(0)-thiyls instead. A wide range of in-situ STM electrochemical and other data is interpreted from this perspective.