Photoredox catalysis enabled by atomically precise metal nanoclusters

Abstract

Atomically precise metal nanoclusters (NCs), distinguished by their unique electronic structures, quantum confinement effects, and enriched active sites, have been considered highly promising photosensitizers for light harvesting and conversion. However, the ultra-short carrier lifetime and poor stability of metal NCs remarkably retard their widespread applications in photocatalysis. In this study, we achieved the modulation of carrier separation over metal NCs via heterostructure engineering by smartly integrating atomically precise silver NCs [Ag₁₆(GSH)₉] with transition metal chalcogenides (TMCs). The favorable energy level alignment between metal NCs and TMCs facilitates the electron transfer from the metal NCs to the TMCs, leading to a significantly prolonged charge lifetime and considerably enhanced photoactivity toward the selective reduction of nitro compounds to amino derivatives under visible light. The photocatalytic mechanism of these composite photosystems is elucidated herein. This work advances our fundamental understanding of charge transfer mechanisms over atomically precise metal NCs for solar energy conversion.