共价有机框架-杂多酸复合材料用于非均相催化烯烃环氧化  

Application of Covalent Organic Framework-Polyoxometalates Composites in Heterogeneous Catalytic Epoxidation of Olefins

作　　者：孔祥宇 廖力 卢灿忠[1,2] 方千荣 KONG Xiangyu;LIAO Li;LU Canzhong;FANG Qianrong(Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350025,China;School of Physical Science and Technology,Shanghai Tech University,Shanghai 201210,China;State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,Jilin University,Changchun 130012,China)

机构地区：[1]中国科学院福建物质结构研究所,福州350025 [2]上海科技大学物质科学与技术学院,上海201210 [3]吉林大学无机合成与制备化学国家重点实验室,长春130012

出　　处：《高等学校化学学报》2023年第12期1-8,共8页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2022YFB3704900,2021YFF0500500);国家自然科学基金(批准号:52073286,22275185,22025504,21621001,22105082)资助.

摘　　要：共价有机骨架是一种结晶性多孔材料,在非均相催化方面有着巨大的应用潜力.本文利用缺电子结构萘二酰亚胺(NDI)的衍生物作为单体,合成了一种新型功能性共价有机框架材料COF-FL-2.COF-FL-2具有较大的孔径和良好的吸附性能,骨架上的NDI结构能通过π-阴离子作用与杂多酸形成稳定的功能性复合材料.通过将磷钨酸(PTA)负载在COF-FL-2上,进一步制备了一种新型杂化杂多酸基复合物[e-mail]@COF-FL-2对以过氧化叔丁醇(t-BuOOH)为氧化剂的烯烃环氧化反应表现出高的催化活性,可以在温和的条件下将环辛烯和1-辛烯环氧化成相应的环氧化物.PTA@COF-FL-2具有出色的稳定性,在反应条件下可长期使用,使用时无PTA浸出现象.此外,PTA@COF-FL-2回收非常方便,可以多次循环使用.Covalent organic frameworks are crystalline porous materials with great application potential in heteroge⁃neous catalysis.We synthesized a new functional covalent organic framework,COF-FL-2,using derivatives of electron-deficient naphthalene diimide(NDI)as monomers.COF-FL-2 has a large pore size and good adsorption performance.The NDI structure on the skeleton can form a stable functional composite with polyoxometalates through π-anion interaction.A novel hybrid heteropolyacid complex,PTA@COF-FL-2,was prepared by loading phosphotungstic acid(PTA)on COF-FL-2.Remarkably,PTA@COF-FL-2 shows high catalytic activity for the epoxidation of olefins with t-BuOOH as the oxidant,and can epoxidate cyclooctene and 1-octene into the corresponding epoxides under mild conditions.PTA@COF-FL-2 can be used for a long time under reaction conditions,and there is no PTA leaching phenomenon when used.In addition,PTA@COF-FL-2 is very convenient to recycle and can be recycled many times.

关 键 词：共价有机框架 杂多酸 非均相催化 负载材料 烯烃环氧化 

分 类 号：O611[理学—无机化学]