Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation

Abstract Ring‐opening of phenol in wastewater is the pivotal step in photocatalytic degradation. The highly selective generation of catalytical active species (•OH) to facilitate this process presents a significant scientific challenge. Therefore, a novel approach for designing photocatalysts with single‐atom containment in metal‐covalent organic frameworks (M‐COFs) is proposed. The selection of imine‐linked COFs containing abundant N and O‐chelate sites provides a solid foundation for anchoring metal atom. These dispersed metal atom possess rapid accumulation and transfer capabilities for photogenerated electrons, while the periodic π‐conjugated structure in 2D‐COFs establishes an effective platform. Additionally, the Lewis acid properties of imine bonds in COFs can enhance the adsorption capacity toward gases with Lewis base properties, such as O 2 and N 2 . It is demonstrated that the Pd 2+ @Tp‐TAPT, designed based on this concept, exhibits efficient oxygen adsorption and follows the reaction pathway of O 2 →•O 2 − →H 2 O 2 →•OH with high selectivity, thereby achieving completely degradation of refractory phenol through photocatalysis within 10 min. It is anticipated that the selective generation of catalytic active species via advanced material design concepts will serve as a significant reference for achieving precise material catalysis in the future.