Thiolate-protected metal nanoparticles containing a few to few hundred metal atoms are interesting materials exhibiting unique physicochemical properties. They encompass the bulk-to-molecule transition region, where discrete electronic states emerge and electronic band energetics yield to quantum confinement effects. Recent progresses in the synthesis and characterization of ultrasmall gold nanoparticles have opened up new avenues for the isolation of extremely monodispersed nanoparticles with atomically precision. These nanoparticles are also called nanoclusters to distinguish them from other regular metal nanoparticles with core diameter >2 nm. These nanoclusters are typically identified by their actual molecular formulas; prominent among these are Au25(SR)18, Au38(SR)24, and Au102(SR)44, where SR is organothiolate. A number of single crystal structures of these nanoclusters have been disclosed. Researchers have effectively utilized density functional theory (DFT) calculations to predict their atomic and electronic structures, as well as their physicochemical properties. The atomically precise metal nanoclusters have been the focus of recent studies owing to their novel size-specific electrochemical, optical, and catalytic properties.In this Account, we highlight recent advances in electrochemistry of atomically precise metal nanoclusters and their applications in electrocatalysis and electrochemical sensing. Compared with gold nanoclusters, much less progress has been made in the electrochemical studies of other metal nanoclusters, and thus, we mainly focus on the electrochemistry and electrochemical applications of gold-based nanoclusters. Voltammetry has been extremely powerful in investigating the electronic structure of metal nanoclusters, especially near HOMO and LUMO levels. A sizable opening of HOMO-LUMO gap observed for Au25(SR)18 gradually decreases with increasing nanocluster size, which is in line with the change in the optical gap. Heteroatom-doping has been a powerful strategy to modify the optical and electrochemical properties of metal nanoclusters at the atomic level. While the superatom theory predicts 8-electron configuration for [Au25(SR)18]- and many doped nanoclusters thereof, Pt- and Pd-doped [PtAu24(SR)18]0 and [PdAu24(SR)18]0 nanoclusters show dramatically different electronic structures, as manifested in their optical spectra and voltammograms, suggesting the occurrence of the Jahn-Teller distortion in these doped nanoclusters. Furthermore, metal-doping may alter their surface binding properties, as well as redox potentials. Metal nanoclusters offer great potential for attaining high activity and selectivity in their electrocatalytic applications. The well-defined core-shell structure of a metal nanocluster is of special advantage because the core and shell can be independently engineered to exhibit suitable binding properties and redox potentials. We discuss recent progress made in electrocatalysis based upon metal nanoclusters tailored for water splitting, CO2 conversion, and electrochemical sensing. A well-defined model nanocatalyst is absolutely necessary to reveal the detailed mechanism of electrocatalysis and thereby to lead to the development of a new efficient electrocatalyst. We envision that atomically controlled metal nanoclusters will enable us to systematically optimize the electrochemical and surface properties suitable for electrocatalysis, thus providing a powerful platform for the discovery of finely tuned nanocatalysts.
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