Heterometal Alloying-Heterostructure Engineering Synergy in Metal Nanoclusters toward Solar-to-Chemical Conversion

High Resolution Image Download MS PowerPoint Slide Atomically precise metal nanoclusters (NCs) have emerged as attractive photosensitizers due to their quantum confinement effect, peculiar atom-stacking mode and abundant active sites. However, conventional monometallic NCs are plagued by ultrashort charge lifetimes, poor photostability, and uncontrolled charge-transport pathways, severely limiting their application in photocatalysis. Herein, we develop a general and robust strategy to overcome these intrinsic obstacles by constructing bimetallic NCs-transition metal chalcogenides (TMCs) artificial photosystems. Glutathione (GSH)-capped alloy NCs (Au 1– x Ag x, Au 1– x Cu x, and Au 1– x Pt x ) are electrostatically self-assembled onto a series of TMCs (CdS, CdIn 2 S 4, ZnIn 2 S 4, and In 2 S 3 ), forming well-defined heterostructures with Type-II band alignment. This configuration enables efficient interfacial charge transfer and spatial charge separation. Therefore, the alloy NCs-TMCs photosystems exhibit markedly enhanced performances across diverse visible-light-driven photoredox reactions, including selective reduction of aromatic nitro compounds, photocatalytic hydrogen evolution, CO 2 reduction, Cr(VI) reduction and hydrogen peroxide generation, outperforming pristine TMCs and their unalloyed counterparts. Mechanism investigations reveal that the heteroatom (Ag, Cu, Pt) doping within Au-based NCs effectively modulates interfacial energy-level alignment, tailors electron transport pathways, suppresses charge recombination, prolongs carrier lifetimes, and significantly reduces interfacial charge-transport resistance. This work elucidates the pivotal role of alloy engineering in governing charge separation in NCs-based artificial photosystems for solar-to-chemical energy conversion.