Modulating the Stacking Model of Covalent Organic Framework Isomers with Different Generation Efficiencies of Reactive Oxygen Species.
Modulating the Stacking Model of Covalent Organic Framework Isomers with Different Generation Efficiencies of Reactive Oxygen Species.
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DOI：
10.1021/acsami.1c03170
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发表时间：
2021-06
影响因子：
9.5
通讯作者：
Shaoxiong Yang;Xia Li;Yu Qin;Yi Cheng;W. Fan;Xianjun Lang;Liyan Zheng;Qiue Cao
中科院分区：
文献类型：
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作者：
Shaoxiong Yang;Xia Li;Yu Qin;Yi Cheng;W. Fan;Xianjun Lang;Liyan Zheng;Qiue Cao
开发一种简便的合成和可控的层堆积方法制备共价有机框架（COFs）是调控其性能和实现其应用多样性的重要问题。本文通过调节反应温度和溶剂介质，得到了具有不同堆积模式（重叠AA、交错AB和ABC堆积）的三种COF异构体。实验和理论计算表明，在室温下得到的ABC堆积异构体是动力学产物，而溶剂热法得到的AA堆积异构体是热力学产物。由于反应过程中涉及的互变异构现象，这些异构体具有不同比例的烯醇和酮形式。因此，它们表现出不同的I型和II型活性氧物质（ROS）产生效率。ABC堆叠异构体可用作无金属的非均相光催化剂，用于可见光诱导的胺氧化为亚胺，由于I型ROS的最高生成效率。
The development of a facile synthesis and controllable layer stacking approach for covalent organic frameworks (COFs) is an important issue for modulating their properties and realizing their application diversity. Herein, three COF isomers with different stacking models (eclipsed AA, staggered AB, and ABC stacking) were obtained by modulating the reaction temperature and solvent medium. Experimental and theoretical calculations show that the ABC stacking isomer obtained at room temperature is the kinetic product, while the AA stacking isomer prepared by the solvothermal method is a thermodynamic product. Owing to the tautomerism involved in the reaction process, these isomers possess different ratios of enol and keto forms. Thus, they exhibit different generation efficiencies of Type I and Type II reactive oxygen species (ROS). The ABC stacking isomers could be employed as metal-free heterogeneous photocatalysts for visible-light-induced oxidation of amines to imines, owing to the highest generation efficiency of Type I ROS.