基于共价有机骨架的固体酸催化剂合成及评价  

Synthesis and evaluation of solid acid catalysts based on covalent organic frameworks

作　　者：胡春洋 单玉华[1] 刘平[1] 王维[1] 李芙蓉 HU Chun-yang;SHAN Yu-hua;LIU Ping;WANG Wei;LI Fu-rong(Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou University,Changzhou 213164,China)

机构地区：[1]常州大学江苏省先进催化与绿色制造协同创新中心,江苏常州213164

出　　处：《现代化工》2020年第10期124-130,共7页Modern Chemical Industry

基　　金：江苏省绿色催化材料与技术重点实验室项目(BM2012110);江苏省科技厅前瞻性研究项目(BY2014037-12)。

摘　　要：利用多苯环单元制备的共价有机骨架材料(COFs)属于磺酸基载体,是用于固体酸催化反应的理想材料。以1,3,5-三苯氧基苯和4,4-二氯甲基联苯为结构单元,通过傅克烷基化反应制备了具有大量磺基接入位点的新型材料(COF-DT),该材料具有较大的比表面积(554 m^2/g)、适当的孔体积(0.35 cm^3/g)与孔径(2.54 nm)和良好的热稳定性与化学稳定性。COFDT表现出优异的磺酸负载能力,改性后的[HSO3]COF-DT酸中心分布均匀,单位磺酸负载量达到4.9 mmol/g,超过传统磺酸基树脂酸量的2倍多。将[HSO3]COF-DT用于催化环己基苯氢过氧化物生产苯酚和环己酮的反应表现出优良的催化效果,原料转化率达到90.8%,环己酮收率为94.3%,苯酚收率为91.1%。在循环使用多次后,依然保持良好的催化活性。Covalent organic frameworks(COFs)prepared by using multiple benzene ring units are ideal sulfonic acid-based supports for solid acid-catalyzed reaction.Using 1,3,5-triphenoxybenzene and 4,4-dichloromethylbiphenyl as structural units,a novel material(named COF-DT)with a large number of sulfo access sites is prepared through Friedel-Crafts alkylation reaction.COF-DT has a large specific surface area(554 m^2·g^-1),suitable pore volume(0.35 cm^3·g^-1)and pore size(2.54 nm),with good thermal stability and chemical stability.It shows excellent sulfonic acid loading capacity.The modified COF-DT([HSO3]COF-DT)has uniform acid center distribution,with a sulfonic acid loading amount of 4.9 mmol·g^-1,more than twice that of traditional sulfo resin.[HSO3]COF-DT can give an excellent catalytic effect when it is used to catalyze the reaction of cyclohexylbenzene hydroperoxide to produce phenol and cyclohexanone.The raw material conversion rate reaches 90.8%,the yields of cyclohexanone and phenol reach 94.3%and 91.1%,respectively.After repeated use,it still maintains good catalytic activity.

关 键 词：磺化 傅克烷基化反应 共价有机框架 固体酸催化剂 非均相 

分 类 号：TQ426[化学工程]