Ultrafast Charge Transfer on Ru‐Cu Atomic Units for Enhanced Photocatalytic H2O2 Production

Abstract Photosensitizer‐assisted photocatalytic systems offer a solution to overcome the limitations of inherent light harvesting capabilities in catalysts. However, achieving efficient charge transfer between the dissociative photosensitizer and catalyst poses a significant challenge. Incorporating photosensitive components into reactive centers to establish well‐defined charge transfer channels is expected to effectively address this issue. Herein, the electrostatic‐driven self‐assembly method is utilized to integrate photosensitizers into metal–organic frameworks, constructing atomically Ru‐Cu bi‐functional units to promote efficient local electron migration. Within this newly constructed system, the Ru(bpy) 2 2+ component and Cu site serve as photosensitive and catalytic active centers for photocarrier generation and H 2 O 2 production, respectively, and their integration significantly reduces the barriers to charge transfer. Ultrafast spectroscopy and in situ characterization unveil accelerated directional charge transfer over Ru‐Cu units, presenting orders of magnitude improvement over dissociative photosensitizer systems. As a result, a 37.2‐fold enhancement of the H 2 O 2 generation rate (570.9 µmol g −1 h −1 ) over that of dissociative photosensitizer system (15.3 µmol g −1 h −1 ) is achieved. This work presents a promising strategy for integrating atomic‐scale photosensitive and catalytic active centers to achieve ultrafast photocarrier transfer and enhanced photocatalytic performance.