Photosensitization by [Mo3S13]2- nanocluster cocatalysts enabling visible-light photocatalytic H2 evolution

Elucidating properties of cocatalysts from all aspects endows them new roles as proactive regulators of light harvesting and reaction kinetics to promote the overall efficiency of photocatalysts. [Mo3S13]2- nanoclusters have served as one of the most efficient catalysts for hydrogen evolution reaction (HER), while their underlying photo-responsive behaviors within hybrid photocatalyst systems remain unexplored. Herein, we unveil the visible-light sensitization effect of [Mo3S13]2- nanoclusters, in the mode of hot electron injection, that drive apparent and sustainable photocatalytic HER. This effect was demonstrated by loading [Mo3S13]2- nanoclusters on wide-bandgap nanosized ZnS host. Detailed characterizations further clarified the photosensitization of [Mo3S13]2- nanoclusters by revealing the dependence of HER activity on the enhanced visible light responsivity and the light-induced nanocluster-to-host electron transfer. This work not only showcases the dual function of the advanced [Mo3S13]2- nanocluster cocatalysts but also provides guidance for the discovery and understanding of more multifunctional materials opening new opportunities for efficient and multi-mode photocatalysis.