Effective combination of the photosensitivity and photothermal capacity in photocatalyst is vital to achieve the maximum light utilization for superior photocatalytic efficiency. Herein, we successfully organize photosensitive Cd-NS single-sites and photothermal Ni-NS single-sites uniformly at a molecular level within a tailored trimetallic metal-organic framework. The optimized Ho6-Cd_0.76Ni_0.24-NS exhibits a superior photocatalytic hydrogen evolution rate of 40.06 mmol g⁻¹ h⁻¹ under visible-light irradiation and an apparent quantum efficiency of 29.37% at 420 nm without using cocatalysts or photosensitizers. A systematical mechanism study reveals that the uniformly organized photosensitive and photothermal single-sites have synergistic effect, which form ultrashort pathways for efficient transport of photoinduced electrons, suppress the recombination of photogenerated charge carriers, hence promote the hydrogen evolution activity. This work provides a promising approach for organizing dual-functional single-sites uniformly in photocatalyst for high-performance photocatalytic activity.

https://onlinelibrary.wiley.com/doi/10.1002/adma.202403464