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Three-Motif Molecular Junction Type Covalent Organic Frameworks for Efficient Photocatalytic Aerobic Oxidation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-01-24 , DOI: 10.1021/jacs.3c12724 Ming-Yi Yang 1 , Shuai-Bing Zhang 2 , Mi Zhang 1 , Ze-Hui Li 1 , Yu-Fei Liu 1 , Xing Liao 1 , Meng Lu 1 , Shun-Li Li 1 , Ya-Qian Lan 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-01-24 , DOI: 10.1021/jacs.3c12724 Ming-Yi Yang 1 , Shuai-Bing Zhang 2 , Mi Zhang 1 , Ze-Hui Li 1 , Yu-Fei Liu 1 , Xing Liao 1 , Meng Lu 1 , Shun-Li Li 1 , Ya-Qian Lan 1
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Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction of functional groups, have aroused broad interest in the field of photocatalysis. However, due to the low light absorption intensity, low photoelectron conversion efficiency, and lack of suitable active sites, it remains a great challenge to achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed a series of three-motif molecular junction type COFs, which formed dual photosensitizer coupled redox molecular junctions containing multifunctional COF photocatalysts. Significantly, due to the strong light adsorption ability of dual photosensitizer units and integrated oxidation and reduction features, the PY-BT COF exhibited the highest activity for photocatalytic aerobic oxidation. Especially, it achieved a photocatalytic benzylamine conversion efficiency of 99.9% in 2.5 h, which is much higher than that of the two-motif molecular junctions with only one photosensitizer or redox unit lacking COFs. The mechanism of selective aerobic oxidation was studied through comprehensive experiments and density functional theory calculations. The results showed that the photoinduced electron transfer occurred from PY and then through triphenylamine to BT. Furthermore, the thermodynamics energy for benzylamine oxidation on PY-BT COF was much lower than that for others, which confirmed the synergistic effect of dual photosensitizer coupled redox molecular junction COFs. This work provided a new strategy for the design of functional COFs with three-motif molecular junctions and also represented a new insight into the multifunctional COFs for organic catalytic reactions.
中文翻译：
用于高效光催化有氧氧化的三基元分子连接型共价有机框架
共价有机骨架（COF）具有灵活的结构调控和易于引入官能团的特点，引起了光催化领域的广泛兴趣。然而，由于光吸收强度低、光电子转换效率低以及缺乏合适的活性位点，实现高效的光催化好氧氧化反应仍然是一个巨大的挑战。在此，基于网状化学，我们合理设计了一系列三基元分子结型COF，形成了含有多功能COF光催化剂的双光敏剂偶联氧化还原分子结。值得注意的是，由于双光敏剂单元的强光吸附能力和集成的氧化和还原特性，PY-BT COF表现出最高的光催化有氧氧化活性。特别是，它在2.5小时内实现了99.9%的光催化苯甲胺转化效率，远高于仅具有一种光敏剂或缺少COF的氧化还原单元的双基元分子连接。通过综合实验和密度泛函理论计算，研究了选择性好氧氧化的机理。结果表明，光诱导电子转移发生在PY，然后通过三苯胺到达BT。此外，PY-BT COF 上苯甲胺氧化的热力学能量远低于其他材料，这证实了双光敏剂耦合氧化还原分子结 COF 的协同效应。这项工作为具有三基序分子连接的功能性COF的设计提供了新的策略，也代表了对用于有机催化反应的多功能COF的新见解。
更新日期：2024-01-24
中文翻译：
用于高效光催化有氧氧化的三基元分子连接型共价有机框架
共价有机骨架（COF）具有灵活的结构调控和易于引入官能团的特点，引起了光催化领域的广泛兴趣。然而，由于光吸收强度低、光电子转换效率低以及缺乏合适的活性位点，实现高效的光催化好氧氧化反应仍然是一个巨大的挑战。在此，基于网状化学，我们合理设计了一系列三基元分子结型COF，形成了含有多功能COF光催化剂的双光敏剂偶联氧化还原分子结。值得注意的是，由于双光敏剂单元的强光吸附能力和集成的氧化和还原特性，PY-BT COF表现出最高的光催化有氧氧化活性。特别是，它在2.5小时内实现了99.9%的光催化苯甲胺转化效率，远高于仅具有一种光敏剂或缺少COF的氧化还原单元的双基元分子连接。通过综合实验和密度泛函理论计算，研究了选择性好氧氧化的机理。结果表明，光诱导电子转移发生在PY，然后通过三苯胺到达BT。此外，PY-BT COF 上苯甲胺氧化的热力学能量远低于其他材料，这证实了双光敏剂耦合氧化还原分子结 COF 的协同效应。这项工作为具有三基序分子连接的功能性COF的设计提供了新的策略，也代表了对用于有机催化反应的多功能COF的新见解。
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