Interfacial Bi–O Bridge Elevated Bi p -Band Center Boosting Photocatalytic C( sp 3 )–H Bonds Oxidation

作者：Xiong Wang, Bing-Hao Wang, Chao Peng, Huijuan Wang, Guang‐Hui Chen, Tian Sheng, Lang Chen, Shuang-Feng Yin · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c02654 · 被引用次数：33 · 研究领域：Advanced Photocatalysis Techniques、Catalytic C–H Functionalization Methods、Catalytic Processes in Materials Science

Photocatalytic selective oxidation of C( sp 3 )–H bonds in hydrocarbons into value-added aldehydes is a promising yet challenging approach due to the higher reactivity of products than reactants. Regulating reactive oxygen species has been proved a feasible way to prevent further oxidation of aldehydes. Herein, uniform Cs 3 Bi 1.8 Sb 0.2 Br 9 (CSBB) nanodots anchored on ultrathin triazine zirconium carboxylate metal–organic layers (ZrTATB) were fabricated through interfacial Bi–O bonds. This not only enhanced the separation of charge carriers but also elevated the Bi p -band center to the Fermi level by generating electron-deficient Bi δ+ sites, which, in turn, reduced the antibonding orbital occupancy of Bi–O ads in the CSBB-ZrTATB composite. Consequently, 1 O 2 as the dominant reactive oxygen species was generated through energy transfer of photoexcited excitons to O 2, whereas •O 2 – over pristine CSBB is more feasible. Notably, the optimized CSBB-75-ZrTATB exhibited an impressive toluene conversion rate of 16,495 μmol g –1 h –1 under solvent-free conditions, with benzaldehyde selectivity maintained as high as 88% over extended light exposure. Moreover, high electrical energy-to-benzyl alcohol and benzaldehyde (ETB) conversion efficiency reached 0.0603%. This work provides insights into the rational construction of chemical bonds to regulate the electronic structure of metal halide perovskites and demonstrates their potential application in photocatalytic aerobic oxidation...