通过改造氧化还原活性位点扩展亚乙烯连接的共价有机框架的不对称π-共轭，用于H2O2光合作用和好氧氧化
{"_":"Extending Asymmetric π-Conjugation of Vinylene-Linked Covalent Organic Frameworks with Remodeled Redox Active Sites for HO Photosynthesis and Aerobic Oxidations.","sub":["2","2"]}
摘要(中文译文)
共价有机框架（COF）在人工光合作用中表现出相当大的潜力，特别是在光还原产生过氧化氢（H2O2）和相关的有氧氧化合成增值化学物质方面。然而，它们的广泛应用受到有限的化学稳定性、次优的氧化还原活性位点和低效的激子解离的阻碍。为了应对这些挑战，我们报告了一种亚乙烯基连接的sp2-COF的设计，通过引入吸电子和极性CN基团（sp2-COF-CN）来扩展不对称π共轭并重塑氧化还原活性位点，以实现优异的H2O2光合作用和好氧氧化反应。综合表征表明，sp杂化C≡N单元的引入重塑了供体-π-受体构型，促进了电荷离域，并显著不对称地提高了电子密度。使用苯甲醇作为牺牲剂，这些效应共同产生了17768.4μmol g-1 h-1的显著H2O2生产率，超过了最近报道的有机和无机光催化剂。此外，sp2-COF-CN在各种好氧氧化反应中表现出高效率，包括糠醇在水中的氧化以及有机溶剂中基于苄胺和硫酚的偶联反应。这项工作表明，扩展sp2-COF的不对称π共轭，结合氧化还原活性位点重塑，可以成为设计高性能非均相光催化剂以选择性合成增值化学品的有效策略。
Abstract
Covalent organic frameworks (COFs) exhibit considerable potential in artificial photosynthesis, notably for photoreductive generation of hydrogen peroxide (HO) and related aerobic oxidative synthesis of value-added chemicals. However, their widespread application is hindered by limited chemical stability, suboptimal redox active sites, and inefficient exciton dissociation. To address these challenges, we report the design of a vinylene-linked sp-COF by introducing an electron-withdrawing and polar -CN group (sp-COF-CN) to extend asymmetric π-conjugation and remodel the redox active sites for achieving superior HO photosynthesis and aerobic oxidation reactions. Comprehensive characterization indicates that the introduction of sp-hybridized C≡N units reshapes the donor-π-acceptor configuration, promotes charge delocalization, and boosts electron density with pronounced asymmetry. These effects collectively yield a remarkable HO production rate of 17,768.4 μmol g h using benzyl alcohol as a sacrificial agent, exceeding those of most recently reported organic and inorganic photocatalysts. Furthermore, sp-COF-CN demonstrates high efficiency in diverse aerobic oxidation reactions, including the oxidation of furfuryl alcohol in water and the benzylamine- and thiophenol-based coupling reactions in organic solvents. This work demonstrates that extending asymmetric π-conjugation of sp-COFs, combined with redox active site remodeling, can be an effective strategy for designing high-performance heterogeneous photocatalysts for the selective synthesis of value-added chemicals.
如何引用
AMA
Xinyi Zhu, Li Chen, Kun Xiong, Yuxuan Kong, Hanqi You, Yujie Wang, et al. {"_":"Extending Asymmetric π-Conjugation of Vinylene-Linked Covalent Organic Frameworks with Remodeled Redox Active Sites for HO Photosynthesis and Aerobic Oxidations.","sub":["2","2"]}. Journal of the American Chemical Society. 2026; doi:10.1021/jacs.6c00731.
APA
Xinyi Zhu, Li Chen, Kun Xiong, Yuxuan Kong, Hanqi You, Yujie Wang, et al (2026). {"_":"Extending Asymmetric π-Conjugation of Vinylene-Linked Covalent Organic Frameworks with Remodeled Redox Active Sites for HO Photosynthesis and Aerobic Oxidations.","sub":["2","2"]}. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.6c00731
GB/T 7714
Xinyi Zhu, Li Chen, Kun Xiong, Yuxuan Kong, Hanqi You, Yujie Wang, et al. {"_":"Extending Asymmetric π-Conjugation of Vinylene-Linked Covalent Organic Frameworks with Remodeled Redox Active Sites for HO Photosynthesis and Aerobic Oxidations.","sub":["2","2"]}[J]. Journal of the American Chemical Society, 2026 doi:10.1021/jacs.6c00731.
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