Pyridyl‐Imine‐Functionalized Donor–Acceptor Covalent Organic Frameworks for Optimal Photosynthesis of Hydrogen Peroxide

作者：Zixuan Li, Bingzi Cai, Ying Zou, Di Zhang, Yizhao Liang, Yibo Zhou, Yu Ma, Xin Wang, Bo Shi, Wen‐Kai Chen, Yuanyuan Liu, Xiaojia Zhao · 发表于：Advanced Energy Materials · 年份：2025 · DOI：10.1002/aenm.202500341 · 被引用次数：55 · 研究领域：Covalent Organic Framework Applications、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

Abstract The artificial photosynthesis of hydrogen peroxide (H 2 O 2 ) using semiconductor photocatalysts is gaining attention as an eco‐friendly and energy‐efficient method. Covalent organic frameworks (COFs) show great promise in enhancing photocatalytic H 2 O 2 production due to their tunable structures and functional diversity. However, the efficiency of H 2 O 2 generation is close to the photoelectric properties of COFs and the microenvironment of their active sites. Herein, the synthesis of pyridyl‐imine‐functionalized COFs (PyIm‐COFs) featuring donor–acceptor (D–A) moieties to improve H 2 O 2 production efficiency is reported. By employing benzothiadiazole (BT) units with varied fluorine substitutions, the electronic environment of the active sites, optimizing the selective two‐electron (2e − ) oxygen reduction reaction (ORR), is tuned. Among the synthesized COFs, PyIm‐BT_F exhibits the highest photocatalytic activity, achieving a H 2 O 2 production rate of 5342 µmol g −1 h −1 . The importance of D–A moieties in the rational design of COF‐based photocatalysts, providing a novel strategy for sustainable H 2 O 2 production through optimized active site environments, is underscored.