Filling the Gap: Atomically Precise Metal Nanoclusters-Induced Z-Scheme Photosystem toward Robust and Stable Solar Hydrogen Generation

Atomically precise metal nanoclusters (NCs) represent a promising generation of metal nanomaterial because of characteristic atomic stacking mode, abundant catalytic active sites, and molecular-like discrete energy band structure. However, crafting metal NCs-dominated photocatalytic systems with mediated charge transport pathways for photoredox catalysis is in the infant stage and their photocatalytic mechanisms remain elusive, which is largely hampered by the ultra-short charge lifetime, generic instability, and complicated electronic structure of metal NCs. In this study, the smart construction of all-solid-state metal NCs-transition metal chalcogenides quantum dots (TMCs QDs) Z-scheme artificial photosystems for robust and stable solar-to-hydrogen conversion is demonstrated. The concurrent favorable photosensitization efficiency of metal NCs and TMCs QDs synergistically stimulate the unexpected Z-scheme charge transport pathway, which significantly boosts the anisotropic spatial vectorial charge transport/separation, giving rise to considerably enhanced visible-light-responsive photocatalytic hydrogen generation performances along with favorable stability. This study would push forward the prosperity of exploring metal NCs-based photosystems for solar-to-hydrogen conversion.