Maneuvering Intrinsic Instability of Metal Nanoclusters for Boosted Solar-Powered Hydrogen Production.

Atomically precise metal nanoclusters (NCs) have recently been unleashed as novel photosensitizers but inevitably suffer from light-induced self-transformation to metal nanocrystals (NYs), leading to substantially reduced photoredox activities. Herein, we conceptually demonstrate how to manipulate the intrinsic instability of metal NCs for smartly crafting long-range cascade charge transfer chain assisted by an ultrathin poly(dialyldimethylammonium chloride) (PDDA) layer that was intercalated at the interface of metal NCs and semiconductor. The unidirectional electron flow endowed by Schottky-type self-transformed metal NYs and unexpected electron-withdrawing capability of PDDA layer concurrently foster the charge transfer cascade, resulting in the markedly enhanced net efficiency of photocatalytic hydrogen evolution performances under visible light irradiation. Our work opens new frontiers for judiciously harnessing the inherent detrimental instability of metal NCs for boosted charge transfer toward solar-to-hydrogen conversion.