Abstract Efficient photocatalytic H2O2 production in organic polymers requires the coordinated regulation of charge separation, O2 activation, and proton delivery, yet these processes are often optimized independently. Here, we report a postsynthetic thiol–yne editing strategy that converts a passive alkynyl bridge in a donor–acceptor covalent organic polymer into a bridge-adjacent proton-responsive catalytic module. Reaction with mercaptoacetic acid transforms the original C═C linkage into a sulfur-containing unit bearing –SCH2COOH groups, thereby reshaping the local reaction environment rather than simply increasing surface polarity. The edited bridge modulates electronic communication, enhances interfacial hydrophilicity, and introduces a reversible COOH/COO– proton-transfer microenvironment under photocatalytic conditions. Combined experimental and theoretical results show that this click-programmed module promotes photogenerated charge separation, strengthens O2 adsorption and activation, facilitates proton-coupled electron transfer, and stabilizes key *OOH intermediates, directing oxygen reduction toward the selective two-electron pathway. Consequently, the edited polymer CP-COOH achieves an H2O2 production rate of 14.959 mmol g–1 h–1 under sacrificial-agent-free conditions using only water and air, representing a 118.7-fold enhancement over the parent polymer. This work establishes backbone bond editing as an effective strategy for programming local reaction fields in organic photocatalysts.
原文链接
分享
引用
