Sodium-Directed Photon-Induced Assembly Strategy for Preparing Multisite Catalysts with High Atomic Utilization...

Integrating different reaction sites offers new prospects to address the difficulties in single-atom catalysis, but the precise regulation of active sites at the atomic level remains challenging. Here, we demonstrate a sodium-directed photon-induced assembly (SPA) strategy for boosting the atomic utilization efficiency of single-atom catalysts (SACs) by constructing multifarious Au sites on TiO₂ substrate. Na⁺ was employed as the crucial cement to direct Au single atoms onto TiO₂, while the light-induced electron transfer from excited TiO₂ to Au(Na⁺) ensembles contributed to the self-assembly formation of Au nanoclusters. The synergism between plasmonic near-field and Schottky junction enabled the cascade electron transfer for charge separation, which was further enhanced by oxygen vacancies in TiO₂. Our dual-site photocatalysts exhibited a nearly 2 orders of magnitude improvement in the hydrogen evolution activity under simulated solar light, with a striking turnover frequency (TOF) value of 1533 h^-1 that exceeded other Au/TiO₂-based photocatalysts reported. Our SPA strategy can be easily extended to prepare a wide range of metal-coupled nanostructures with enhanced performance for diverse catalytic reactions. Thus, this study provides a well-defined platform to extend the boundaries of SACs for multisite catalysis through harnessing metal-support interactions.