Four fundamental reactions are essential to harnessing energy from water sustainably: oxidation reduction reaction (ORR), oxygen reduction reaction (OER), hydrogen oxidation reaction (HOR), and hydrogen evolution reaction (HER). This review summarizes the research advancements in the electrocatalytic reaction of metal nanoclusters for water splitting. It covers various types of nanoclusters, particularly those at the size level, that enhance these catalytic reactions. The synthesis of cluster-based catalysts and the elucidation of the structure-activity relationships and reaction mechanisms are discussed. Emphasis is placed on utilizing atomically precise cluster materials and the interplay between the carrier and cluster in water catalysis, especially for applying catalytic engineering principles (such as synergy, coordination, heterointerface, and lattice strain engineering) to understand structure-activity relationships and catalytic mechanisms for cluster-based catalysts. Finally, the field of cluster water catalysis is summarized and prospected. We believe that developing cluster-based catalysts with high activity, excellent stability, and high selectivity will significantly promote the development of renewable energy conversion reactions.
Keywords: Cluster catalysis; hydrogen evolution reaction; hydrogen oxidation reaction; oxidation reduction reaction; oxygen reduction reaction.