Porous Organic Frameworks with Integrative Task-Specific O 2 /H 2 O Active Sites and Donor–Acceptor Dyads for Photocatalytic H 2 O 2 Generation

作者：Xiahong Xu, Dandan Jiang, Kangle Xie, Yan Sui, Wen‐Tong Chen, Yuntong Li, Hong Zhong, He‐Rui Wen · 发表于：ACS Applied Polymer Materials · 年份：2025 · DOI：10.1021/acsapm.5c00514 · 被引用次数：8 · 研究领域：Advanced Photocatalysis Techniques、Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications

The photocatalytic generation of hydrogen peroxide (H 2 O 2 ) through the reduction of oxygen (O 2 ) coupled with the oxidation of water (H 2 O) represents a green and sustainable alternative to the traditional anthraquinone process, but the ability is inevitably tied to the task-specific active sites and the light-harvesting range. Herein, a porous organic framework (TEADP-POF) containing integrative task-specific catalytic active sites and donor–acceptor dyads structure was prepared through tris(4-ethynylphenyl)amine (TEA) reacting with 2,5-dibromopyridine (DP). The triphenylamine moieties being electron-donating and pyridine moieties being electron-withdrawing, their electron push and pull effect could widen the range of light harvesting and accelerate photoinduced charges’ separation and migration. The carbon atoms next to pyridinic N can adsorb and activate the O 2 molecule; meanwhile, the nitrogen atoms of triphenylamine moieties could weaken the H 2 O molecule by hydrogen bond interactions. These spatially separated task-specific catalytic active sites lead to efficient charge separation for the respective O 2 reduction half-reaction and H 2 O oxidation half-reaction. The TEADP-POF with task-specific O 2 and H 2 O active sites and donor–acceptor dyads structure enables it to maximize photoinduced charge utilization and shows high-efficiency photocatalytic generation of H 2 O 2, of which the initial rate is as high as 2136 μmol g –1 h –1 under visible-light (λ ≥ 400 nm)...