Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis

作者：Youxing Liu, Lu Li, Hao Tan, Na Ye, Yu Gu, Shuoqing Zhao, Shipeng Zhang, Mingchuan Luo, Shaojun Guo · 发表于：Journal of the American Chemical Society · 年份：2023 · DOI：10.1021/jacs.3c05914 · 被引用次数：201 · 研究领域：Advanced Photocatalysis Techniques、Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field of photosynthesis of hydrogen peroxide (H 2 O 2 ). Despite recent important endeavors, weak confinement of MICs in the reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy of fluorinated covalent organic frameworks (COFs) to strongly confine Pd ICs for greatly boosting the photocatalytic activity and stability of H 2 O 2 photosynthesis. Both experimental and theoretical results reveal that strong electronegative fluorine can increase the metal–support interaction and optimize the d-band center of Pd ICs, thus significantly enhancing the stability and activity of photocatalytic H 2 O 2 . An optimal TAPT-TFPA COFs@Pd ICs photocatalyst delivers a stable H 2 O 2 yield rate of 2143 μmol h –1 g –1 . Most importantly, the as-made TAPT-TFPA COFs@Pd ICs exhibit high catalytic stability over 100 h, which is the best among the reported materials.