文献类型：期刊文献

英文题名：The Redox Cycle of Viologen-Based Porous Organic Polymers for High-Performance Hydrogen Peroxide Photosynthesis

作者：Wu, Chenxi[1];Feng, Shufan[1];Hu, Huaicong[2,3];Zhang, Jiayi[1];Zhang, Xiaolong[1];Wang, Zhiqiang[2,3];Hua, Jianli[1]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ch, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn &Ind Catalysis, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai, Peoples R China

年份：2025

卷号：31

期号：25

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20251418185847);WOS:【SCI-EXPANDED(收录号:WOS:001483043500006)】；

基金：For financial support of this research, the authors thank the projects supported by the National Natural Science Foundation of China (22271093 and 21971064), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the Fundamental Research Funds for the Central Universities (222201717003 and 50321101918001) and the Programme of Introducing Talents of Discipline to Universities (B16017). The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

语种：英文

外文关键词：artificial photosynthesis; hydrogen peroxide; redox; viologen moiety

摘要：Harnessing solar energy to produce hydrogen peroxide (H2O2) is an important strategy to address the current energy shortage. Among various materials, porous organic polymers (POPs) stand out as promising candidates for photocatalytic H2O2 generation due to their versatile structures and extended pi-conjugation; however, their efficiency in H2O2 synthesis is often constrained by poor charge separation and high reaction energy barriers. To address these challenges, we drew inspiration from the redox reactions of coenzyme NADPH in natural photosynthesis, the redox-active methyl viologen (MV2+) moiety was rationally incorporated into two polymer frameworks (TPE-MV and TPB-MV) as pivotal active sites for photocatalytic oxygen (O2) reduction to H2O2 via the reversible redox cycle of MV2+ and zerovalent methyl viologen (MV0). Through this redox cycle, MV2(+) accepts two photogenerated electrons, reducing it to MV0. MV0 sequentially reduces O-2 to H2O2 while regenerating MV2(+). Mechanistic studies show that this approach effectively suppresses charge recombination and lowers the reaction energy barriers. Consequently, the photocatalytic H2O2 generation rates of TPE-MV and TPB-MV reached 6068 and 2015 mu mol g(-1) h(-1), respectively. This work offers a new strategy for designing efficient photocatalysts by incorporating biomimetic redox-active moieties to enhance solar energy utilization for H2O2 production.