Atomically Precise Metal Nanoclusters versus Metal Nanocrystals: Maneuvering Tunable Charge Transfer in an Integrated Photosystem.

Atomically precise metal nanoclusters (NCs) have recently emerged as a promising sector of metal nanomaterials in terms of peculiar atomic stacking fashion, quantum confinement effect, and enriched catalytically active sites, which are wholly distinct from conventional metal nanocrystals (NYs) in all respects. However, atomically precise metal NCs inevitably suffer from intrinsic poor instability either under light irradiation or thermal treatment owing to the ultrahigh surface energy, thereby resulting in substantial loss of photosensitization efficiency and retarding their emerging utilization in photoredox catalysis. Here, we first conceptually reveal the charge transfer characteristic difference between atomically precise metal NCs and metal NYs attained by self-transformation in boosting interfacial charge migration and separation. The results signify that the interfacial charge transfer impetus of atomically precise metal NCs as a photosensitizer versus metal NYs as a Schottky-type electron-withdrawing mediator is closely associated with the loading amount on the semiconductor substrate. The photosensitization effect of atomically precise metal NCs is superior to the electron trapping capability of metal NYs when the loading amount of the metal ingredient is relatively high and vice versa. Our work would significantly bridge the gap between atomically precise metal NCs and metal NYs in fine tuning of the charge transfer pathway in photocatalysis toward solar energy conversion.