Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation
Yang, Liujun1,Chen, Chen, Zhengxi1, Cao, Qiang1, Liao, Huarong1, Gao, Jin1, Zhang, Long1, Wei, Wanyu1, Li, Hua1,2（李华）, Lu, Jianmei1,2（路建美）
1College of Chemistry Chemical Engineering and Materials Science, Collaborative Innovation Center of Suzhou Nano Science and Technology Soochow University, Suzhou, Jiangsu 215123, China
2National Center of International Research on Intelligent New Nanomaterials and Detection Technologies in Environmental Protection Suzhou, Jiangsu 215123,China
Adv. Mater. 2023, 2306758
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-chelatesites 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 O2 and N2. It is demonstrated that the Pd2+@Tp-TAPT, designed based on this concept, exhibits efficient oxygen adsorption and follows the reaction pathway of O2→•O2−→H2O2→•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.
链接：//onlinelibrary.wiley.com/doi/epdf/10.1002/adma.202306758
