Condensation Center Regulation in Donor–Acceptor Polymers Enables Dynamic Proton Reservoirs for Efficient H 2 O 2 Photosynthesis

作者：Fanzhi Qin, Chen Zhang, Deyu Qin, Hao Weng, Abing Duan, Hou Wang, Danlian Huang, Lin Tang, Yuqin Zou, Guangming Zeng, Shuangyin Wang · 发表于：Journal of the American Chemical Society · 年份：2026 · DOI：10.1021/jacs.6c00799 · 被引用次数：2 · 研究领域：Photosynthetic Processes and Mechanisms、Advanced battery technologies research、Metal-Catalyzed Oxygenation Mechanisms

Photocatalytic hydrogen peroxide production offers a sustainable route for solar-to-chemical energy conversion, yet precise control over structure–reactivity relationships in organic photocatalysts remains limited. Here, we report diazine-based donor–acceptor (D–A) imine-linked covalent organic polymers (COPs) designed for efficient H 2 O 2 generation. By regulating the condensation centers (para, meta, and ortho), we find that para-regulated polymers exhibit the highest structural stability and photocatalytic reactivity. Mechanistic and theoretical analyses reveal that H 2 O 2 photosynthesis is dominated by indirect 2 e – oxygen reduction reaction (ORR) and complemented by a 4 e – water oxidation reaction (WOR), alleviating the dependence on O 2 -rich environments. Importantly, localized protonation is shown to be essential for O 2 adsorption and activation, with Pauling-type end-on binding favoring selective 2 e – ORR. In addition, −CN incorporation and para-regulation effectively lower the rate-limiting energy barriers, strengthening interfacial electron transfer. Dynamic proton reservoir behavior further endows the system with broad pH adaptability, maintaining stable local proton levels throughout the reaction. This work highlights the importance of condensation center regulation in programming reactant activation and charge transfer behavior, providing a design principle for advanced COPs in artificial photosynthesis.