Hanxi Li, Zhi‐Gang Li, Xinghao Zhang, Hui Jiao, Haichao Wang, Zhenhai Fan, Yutong Wang, Yuan Li, Jijie Zhang, Xian‐He Bu
ABSTRACT Raising electron transfer efficiency is a crucial issue in improving photocatalytic productivity. Herein, we propose a strategy for anchoring single atoms and the establishment of a short‐distance electron transport pathway. By incorporating nitrogen‐containing monodentate ligands into UIO‐66‐NH 2 , Pt single atom could be co‐anchored by both the nitrogen atom and the vacant Zr‐oxo cluster. Subsequently, the Pt‐containing UIO was condensed with TpPa‐1. Thereby, a molecular‐level electron transfer pathway from TpPa to Pt has been established at the heterointerface between TpPa and UIO. By rationally adjusting the positions of the functional groups (‐H, ‐Cl, and ‐OCH 3 ) in the monodentate ligand, their involvement in the pathway was precisely regulated. They functioned as electron relays when positioned at the ortho‐position of the amino group, thereby facilitating the electron delivery. Cl exhibited a more pronounced effect compared to OCH 3 , UPT‐ o ‐Cl achieved the maximum H 2 yield of 14.21 mmol g −1 h −1 . Mechanism calculations revealed that the groups located along the pathway would regulate the microenvironment of the constructed tunnels, resulting in a higher electron density and enhanced ability to adsorb H intermediates of the Pt sites. This research reports a strategy for precisely regulating the microenvironment adjacent to the active site, providing new insights into enhancing carrier mobility and utilization efficiency.