Alloy Metal Nanocluster: A Robust and Stable Photosensitizer for Steering Solar Water Oxidation

Metal nanoclusters (NCs) have been unleashed as an emerging category of metal materials by virtue of integrated merits including the unusual atom-stacking mode, quantum confinement effect, and fruitful catalytically active sites. Nonetheless, development of metal NCs as photosensitizers is blocked by light-induced instability and ultrashort carrier lifespan, which remarkably retards the design of metal NC-involved photosystems, hence resulting in the decreased photoactivities. To solve these obstacles, herein, we conceptually probed the charge transfer characteristics of the BiVO₄ photoanode photosensitized by atomically precise alloy metal NCs, wherein tailor-made l-glutathione-capped gold-silver bimetallic (AuAg) NCs were controllably self-assembled on the BiVO₄ substrate. It was uncovered that alien Ag atom doping is able to effectively stabilize the alloy AuAg NCs and simultaneously photosensitize the BiVO₄ photoanode, significantly boosting the photoelectrochemical (PEC) water oxidation performances. The reasons for the robust and stable PEC water oxidation activities of the AuAg NCs/BiVO₄ composite photoanode were unambiguously unleashed. We ascertain that Ag atom doping in the staple motif of Au_x NCs efficaciously protects the NCs from rapid oxidation, enhancing the photostability, boosting the photosensitization efficiency, and thus leading to the considerably improved PEC water splitting activities compared with the homometallic counterpart. This work could afford a new strategy to judiciously tackle the inherent detrimental instability of metal NCs for solar energy conversion.