Heteroatom-Bridged Covalent Organic Frameworks for Efficient Solar-Driven H 2 O 2 Production through Tailored Electronic Structures

作者：Xiaomin Wu, Dandan Lin, Yanlei Zhou, Yuting Xiao, Shien Guo, Peng Yu, Ren‐Jie Song · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2025 · DOI：10.1021/acssuschemeng.5c06983 · 被引用次数：12 · 研究领域：Covalent Organic Framework Applications、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

Covalent organic frameworks (COFs) exhibit significant potential for solar-driven H 2 O 2 synthesis but are intrinsically limited by inefficient charge separation and sluggish oxygen reduction reaction kinetics. In this study, we developed a heteroatom-bridging strategy for the precise atomic engineering of pyrene-based COFs (PX-COFs, X = C/O/S). The strategic substitution of bridging atoms with oxygen or sulfur effectively modulates the electronic configuration and optimizes reaction thermodynamics. The resulting PO-COF demonstrates an exceptional visible-light-driven H 2 O 2 production rate of 3446.3 μmol g –1 h –1, surpassing the performance of most reported COF-based photocatalysts. Comprehensive characterization combined with density functional theory calculations reveals that the superior activity arises from synergistic effects: enhanced light harvesting, thermodynamically favorable O 2 adsorption coupled with a reduced energy barrier for *OOH intermediate formation, and accelerated interfacial charge transfer kinetics. Crucially, we establish a clear correlation between the electronegativity of the bridging heteroatom and the photocatalytic activity, identifying oxygen as uniquely capable of synchronizing light harvesting, charge separation, and surface catalysis. This work provides fundamental insights for the rational design of highly efficient COF-based photocatalysts to advance solar-to-chemical energy conversion.