Boosting Visible-Light-Driven Photocatalytic Hydrogen Production through Sensitizing TiO₂ via Novel Nanoclusters

Improving the light utilization and electron-hole separation efficiency plays a central role in photocatalysis for converting light energy to hydrogen energy. Herein, for the first time, a stable, highly dispersible discrete T4 [Cd₃In₁₇Se₃₁]^5- cluster is developed as a novel photosensitizer to sensitize TiO₂ for photocatalytic hydrogen production. Compared with pristine TiO₂ (near zero) and the T4 clusters (19.5 μmol g^-1 h^-1) that exhibit low hydrogen evolution activities, the T4/TiO₂ composite, constructed from traces of 0.127 mol % T4 cluster-sensitized TiO₂, exhibits a dramatically improved photocatalytic activity of 328.2 μmol g^-1 h^-1, highlighting that the photocatalytic efficiency strongly correlates with that of the T4 cluster. In the meantime, the T4/TiO₂ composites are highly stable, remaining robust in a long-time test of 50 h for photocatalytic hydrogen production. Ultrafast transient absorption spectroscopy, in combination with electrochemical analyses, steady-state and time-resolved photoluminescence, and density functional theory calculations, indicates that the T4 cluster not only serve as a photosensitizer to absorb visible light but also form a heterojunction between the interface of the T4 cluster and TiO₂ to accelerate electron injection. This work highlights the great potential of the stable and highly dispersed discrete metal chalcogenide clusters as high-efficiency photosensitizers for converting solar energy to chemical energy.