光催化有机反应中的共价有机框架材料  

Covalent Organic Frameworks in Photocatalytic Organic Reactions

作　　者：王静怡 许昕 郑仕佳 魏丕峰 安万凯[2] Jingyi Wang;Xin Xu;Shijia Zheng;Pifeng Wei;Wankai An(School of Chemistry&Chemical Engineering,Linyi University,Linyi 276000,China;College of Science,Henan Agricultural University,Zhengzhou 450002,China)

机构地区：[1]临沂大学化学化工学院,临沂276000 [2]河南农业大学理学院,郑州450002

出　　处：《化学进展》2024年第5期645-666,共22页Progress in Chemistry

基　　金：山东省自然科学基金项目(No.ZR2020QB038);国家自然科学基金项目(No.21702049);河南农业大学科技创新基金(No.2023CXZX006)资助。

摘　　要：共价有机框架(COFs)由于其优异的光催化活性成为多孔材料领域的研究热点。与其他多相光催化剂相比,COFs具有规整且可控的结构、大的比表面积、均匀的孔道、良好的稳定性、可回收利用性、合适的能带结构、可调节的吸光范围和易于功能化等优点,使其具有更高的研究潜力和工业化应用价值。近年来COFs在光催化领域的应用突飞猛进,尤其是在光催化有机反应方向取得了巨大进展,极大地促进了COFs的发展。本综述简单介绍一些光功能化COFs的合成策略,如:自下而上(bottom-up)的策略、后修饰方法和复合法,然后总结了COFs光催化反应机理分为能量转移和电子转移两种途径,而后重点总结和讨论COFs作为光催化剂在光催化选择性氧化反应、还原反应、偶联反应、环化反应、聚合反应和不对称有机合成等反应中的最新研究进展,最后对COFs在光催化有机反应中的应用进行总结和展望。Covalent organic frameworks(COFs)have become one of the research focuses currently in porous materials due to their excellent photocatalytic activity.Compared with other heterogeneous photocatalysts,COFs possess regular and controllable structures,large specific surface areas,uniform pore channels and good chemical/thermal stability.Additionally,COFs have suitable band structures,adjustable absorption range,and are easy to be functionalized and recovered/reused after the reactions.The advantages above surely endow COFs with potential value in fundamental researches and industrial applications.In recent years,the application of COFs in photocatalysis has gained rapid progress,especially in the field of photocatalytic organic transformations.Theses significant works have greatly promoted the development of COFs.In this review,numerous synthesis strategies for photo-functionalized COFs are briefly introduced,e.g.,“bottom-up”strategy,post modification and combination method.Then,the photocatalytic reaction mechanisms mediated by COFs are condensed into two pathways,i.e.,energy transfer and electron transfer.The latest research progress of COFs as photocatalysts in photocatalytic selective oxidation reaction(oxidation of amines to imines,preparation of sulfoxides through selective oxidation of sulfides,oxidation hydroxylation of arylboronic acids to phenols,and oxidation of N-aryl tetrahydroisoquinoline),reduction reaction(reductive dehalogenation,hydrogenation of nitrobenzene,and hydrogenation of styrene),coupling reaction(C-C cross-dehydrogenative coupling reaction,C−N cross-coupling reaction,and C−S cross-coupling reaction),cyclization reaction,polymerization reaction and asymmetric organic synthesis,etc.,are succinctly outlined and discussed.Finally,the application of COFs in photocatalysis is summarized and prospected.

关 键 词：共价有机框架 光催化 氧化反应 还原反应 偶联反应 环化反应 不对称有机合成 

分 类 号：O644.1[理学—物理化学] O643.3[理学—化学] O632