The ligand effect on the interface structures and electrocatalytic applications of atomically precise metal nanoclusters

Abstract Metal nanoclusters, also known as ultra-small metal nanoparticles, occupy the gap between discrete atoms and plasmonic nanomaterials, and are an emerging class of atomically precise nanomaterials. Metal nanoclusters protected by different types of ligands, such as thiolates, alkynyls, hydrides, and N-heterocyclic carbenes, have been synthesized in recent years. Moreover, recent experiment and theoretical studies also indicated that the metal nanoclusters show great promise in many electrocatalytic reactions, such as hydrogen evolution, oxygen reduction, and CO 2 reduction. The atomically precise nature of their structures enables the elucidation of structure-property relationships and the reaction mechanisms, which is essential if nanoclusters with enhanced performances are to be rationally designed. Particularly, the ligands play an important role in affecting the interface bonding, stability and electrocatalytic activity/selectivity. In this review, we mainly focus on the ligand effect on the interface structure of metal nanoclusters and then discuss the recent advances in electrocatalytic applications. Furthermore, we point out our perspectives on future efforts in this field.