分子氧环氧化烯烃多相催化剂PCuMo_(11)/富氮类共价有机骨架材料的制备及应用  

Preparation and application of heterogeneous catalyst PCuMo_(11)/nitrogen rich covalent organic framework material for olefin epoxidation with molecular oxygen oxidant

作　　者：高文秀[1] 吕杰琼 邢树宇 谢晖 高永平 娄大伟[1] GAO Wenxiu;LV Jieqiong;XING Shuyu;XIE Hui;GAO Yongping;LOU Dawei(School of Chemical and Pharmaceutical Engineering,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院化学与制药工程学院,吉林132022

出　　处：《复合材料学报》2022年第10期4701-4708,共8页Acta Materiae Compositae Sinica

基　　金：吉林省科技发展计划项目(2020122373JC);吉林省产业技术研究与开发项目(No.2020C028-1);吉林省教育厅科研规划项目(JJKH20200240KJ);吉林市科技局杰出青年人才培养项目(201831757);吉林省精细化工重点实验室(20140622023JC)。

摘　　要：环氧化合物是一类重要的有机合成中间体和化工原料,主要通过烯烃环氧化反应获得。制备在分子氧环境下高效、稳定、可重复使用的烯烃环氧化反应新型催化剂是一项十分有意义的工作。以富氮类共价有机骨架材料(PC)为载体,多金属氧酸盐PCuMo_(11)为活性物质,制备了复合材料PCuMo_(11)/PC。通过FT-IR、N吸附脱附、XPS、TEM及EDS等测试对材料进行了表征,并将PCuMo_(11)/PC应用于多相催化分子氧气氛下的烯烃(苯乙烯、1-辛烯、环辛烯和环十二烯)环氧化反应中,取得了较高的催化活性和选择性,循环使用5次以上催化活性没有明显下降。实验结果显示,二维层状富氮类共价有机骨架材料的高表面积及骨架中丰富的氮元素含量,有利于均匀地分散催化活性物质多金属氧酸盐,并与其建立相对稳定的化学链接,提高复合材料的催化活性及稳定性。Epoxide is an important organic synthesis intermediate and chemical raw material that is mainly prepared from the olefin epoxidation. It is a very interesting work to prepare efficient catalysts with stability and recyclability for aerobic olefins epoxidation. Composite PCuMo_(11)/PC was prepared by using the nitrogen rich covalent organic framework material(PC) as support and the polyoxometalate PCuMo_(11)as active substance. The materials were characterized by FT-IR, Nadsorption and desorption, XPS, TEM and EDS. The application of PCuMo_(11)/PC for heterogeneous catalytic epoxidation of olefins(styrene, 1-octene, cyclooctene, cyclododecene) with molecular oxygen oxidant has obtained high catalytic activity and selectivity. There is no significant decrease in catalytic activity after recycling over five times. The experimental results show that large surface area and rich nitrogen content in the skeleton of the two-dimensional layered nitrogen rich covalent organic framework material are benefit to disperse the catalytic active substance polyoxometalate uniformly and establish a relatively stable chemical link, so as to improve the catalytic activity and stability of the composite.

关 键 词：共价有机骨架材料(COF) 多金属氧酸盐(POM) 复合材料 催化剂 烯烃 环氧化 

分 类 号：O643.36[理学—物理化学]