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

Abstract

Elucidating the properties of cocatalysts from all aspects endows them with new roles as proactive regulators of light harvesting and reaction kinetics, thereby promoting 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 via hot-electron injection, driving apparent and sustainable photocatalytic HER. This effect was demonstrated by loading [Mo₃S₁₃]²⁻ nanoclusters on a wide-bandgap nanosized ZnS host. Detailed characterizations further clarified the photosensitization of [Mo₃S₁₃]²⁻ nanoclusters, revealing that HER activity is enhanced by visible-light responsivity and 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, multimodal photocatalysis.