Pd负载羟基多孔有机聚合物催化硅烷与醇脱氢偶联反应  

Pd-supported hydroxyl porous organic polymers for catalysis on dehydrogenation coupling reaction of silanes and alcohols

作　　者：王和荣 刘森群 陈家尧 廖兴才 曾蓉 丁顺民[1] WANG Herong;LIU Senqun;CHEN Jiayao;LIAO Xingcai;ZENG Rong;DING Shunmin(School of Chemistry and Chemical Engineering,Nanchang University,Nanchang 330031,Jiangxi,China;School of Chemistry and Materials Science,East China University of Technology,Nanchang 330013,Jiangxi,China)

机构地区：[1]南昌大学化学化工学院,江西南昌330031 [2]东华理工大学化学与材料学院,江西南昌330013

出　　处：《精细化工》2025年第4期858-864,917,共8页Fine Chemicals

基　　金：国家自然科学基金项目(22002056、22262022);江西省自然科学基金项目(20232BAB203016、20232BAB203013)。

摘　　要：甲苯、苯酚和邻苯二酚分别通过Friedel-Crafts反应制备了3种多孔有机聚合物(POP)载体,通过浸渍和还原法将Pd纳米粒子负载在POP载体上,制备了3种羟基质量分数不同的Pd/POP催化剂。采用FTIR、XRD、XPS、SEM、TEM对催化剂的组成、结构和形貌进行了表征,探究了催化剂表面羟基质量分数对Pd/POP催化剂催化二甲基苯基硅烷(硅烷)与乙醇脱氢偶联合成二甲基苯基乙氧基硅烷(硅醚)反应的影响。结果表明,Pd/POP催化剂表现出良好的催化活性,硅烷转化率和硅醚选择性均达到99%;催化剂表面羟基质量分数越高,与Pd纳米粒子的相互作用越强,催化剂循环稳定性越好,以邻苯二酚为单体制备的催化剂Pd/POP-OH-2循环7次后,硅烷转化率和硅醚选择性未明显改变;Pd/POP-OH-2适用于多种硅烷(苯硅烷、二苯基硅烷、三苯基硅烷)与醇(甲醇、乙醇、正丙醇、异丙醇或正丁醇)的脱氢偶联反应,目标硅醚产率在34%~99%之间。Three types of Pd/POP catalysts with different hydroxyl mass fractions were prepared by loading Pd nanoparticles via impregnation and reduction methods onto three porous organic polymer(POP)supports,which were synthesized from simple Friedel-Crafts reaction of toluene,phenol and hydroquinone,respectively,and characterized by FTIR,XRD,XPS,SEM and TEM for analyses on composition,structure and morphology.The effect of surface hydroxyl mass fraction in the Pd/POP catalyst on the dehydrogenation coupling reaction of dimethyl phenyl silane(silane)with ethanol to form dimethyl phenyl ethoxysilane(silane)was evaluated.The results showed that the Pd/POP catalyst exhibited good catalytic activity,silane conversion and silane ether selectivity reached 99%.Higher hydroxyl group mass fraction on the catalyst surface led to stronger interaction with Pd nanoparticles,and better cyclic stability.When Pd/POP-OH-2 catalyst prepared with catechol as monomer was recycled 7 times,the silane conversion and silane ether selectivity did not change significantly.Pd/POP-OH-2 was suitable for the dehydrogenation coupling reaction of various silanes(phenylsilane,diphenylsilane,triphenylsilane)and alcohols(methanol,ethanol,n-propanol,isopropanol or n-butanol),with the target silane yield ranging from 34%to 99%.

关 键 词：羟基多孔有机聚合物 Pd纳米催化剂 硅烷 脱氢偶联 硅醚 

分 类 号：TQ203.2[化学工程—有机化工]