Ultrasmall metal nanoclusters (NCs) with atomic precision occupy a size range between individual atoms and plasmonic nanomaterials. These atomically precise materials represent an emerging class of nanocatalysts, offering unique opportunities to explore the electrocatalytic properties and establish the precise structure-property correlations at the atomic scale. Among the large number of metal NCs stabilized by various ligands, the thiolate-protected metal NCs are a particularly prominent class for electrocatalysis investigation. Recent experimental and theoretical studies have demonstrated the significant potential of these materials in enhancing various electrocatalytic reactions, including hydrogen evolution, oxygen reduction and CO2 reduction. However, comprehensive and in-depth discussions, particularly from a theoretical standpoint, regarding their catalytic properties remain limited and require further exploration. In this review, we focus on the recent progress of thiolate-protected metal NCs in the field of electrocatalysis. The influences of structure, ligand, doping and interface control on the electrocatalytic activity/selectivity, as well as the reaction mechanism are discussed. Importantly, the perspectives we propose regarding future research endeavors are expected to offer valuable references for subsequent investigations in this area.
