In situ etching-induced self-assembly of metal cluster decorated one-dimensional semiconductors for solar-powered water splitting: unraveling cooperative synergy by photoelectrochemical investigations.

Although recent years have witnessed considerable progress in the synthesis of metal clusters, there is still a paucity of reports on photoelectrochemical (PEC) properties of metal cluster/semiconductor systems for solar energy conversion. In this work, highly ordered glutathione (GSH)-protected gold (Au) cluster (Aux@GSH) enwrapped ZnO nanowire array (NW) heterostructures (Aux/ZnO NWs) were designed by a facile, green, simple yet efficient in situ etching-induced electrostatic self-assembly strategy by modulating the intrinsic surface charge properties of building blocks, which renders negatively charged Aux clusters spontaneously and uniformly self-assembles them on positively charged ZnO NWs framework with intimate interfacial integration. It was unraveled that such Aux/ZnO NWs heterostructures demonstrated significantly enhanced PEC water splitting performance in comparison with single ZnO NWs, Au nanoparticles (Au/ZnO NWs) and GSH-capped Agx clusters (Agx/ZnO NWs) decorated ZnO NWs counterparts under both simulated solar and visible light irradiation. The vitally important role of Aux clusters as photosensitizer was unambiguously revealed and the merits of Aux clusters in boosting charge transfer arising from their unique core-shell architecture were highlighted by systematic comparison under identical conditions, based on which Aux cluster-mediated PEC water splitting mechanism is delineated. It is anticipated that our work can highlight the possibility of harnessing metal clusters as efficient light-harvest antennas and open new avenues for rational construction of various highly energy efficient metal cluster/semiconductor heterostructures for widespread photocatalytic and PEC applications.