手性钨酸离子液体空心介孔硅球用于苯乙烯双羟化反应  

Chiral tungstic ionic-liquid hollow mesoporous silica spheres for dihydroxylation of styrene

作　　者：郭晓萍 孟慧琴 焦勇霞 王晓春 王俊飒 梁栋 GUO Xiaoping;MENG Huiqin;JIAO Yongxia;WANG Xiaochun;WANG Junsa;LIANG Dong(School of Chemical Engineering and Technology,North University of China,Taiyuan 030051,Shanxi,China;Taiyuan Ecological Environment Monitoring Center,Taiyuan 030002,Shanxi,China)

机构地区：[1]中北大学化学工程与技术学院,山西太原030051 [2]太原生态环境监测中心,山西太原030002

出　　处：《精细化工》2022年第8期1654-1661,共8页Fine Chemicals

基　　金：国家自然科学基金项目(21406211,21407101,22176117);山西省自然科学基金项目(201901D111171)。

摘　　要：以1,12-二溴十二烷、(S)-烟碱和二水合钨酸钠为原料制备手性钨酸离子液体,再以九水合硅酸钠为硅源,经一步水热法制得含手性多酸离子液体的功能化空心介孔硅球。用SEM、TEM、FTIR、UV-Vis、N吸附-脱附、XPS、电感耦合等离子体发射光谱(ICP-OES)、水接触角和圆二色谱对其进行表征,并考察其对于苯乙烯双羟化反应的催化性能。结果表明,空心介孔硅球的平均直径约为100 nm,比表面积为20~54 m^(2)/g,平均孔径为7.73~15.98 nm;手性钨酸离子液体成功嵌入到空心介孔硅球壳层,固体具有圆二色性,可用于苯乙烯双羟化反应,由n(W)∶n(Si)=0.25∶0.75制得的催化剂催化性能最好、反应3 h(R)-苯基乙二醇产率达89.6%,使用5次后产率仍可达87.0%;未含钨酸离子液体的样品为无定形纳米颗粒,因此推测钨酸基手性离子液体对空心介孔硅球形成具有导向作用。Hollow mesoporous silica spheres functionalized with chiral tungstic ionic liquid in various ratios were synthesized via one-step hydrothermal reaction between sodium silicate nonahydrate and chiral tungstic ionic liquid,which was prepared from 1,12-dibromododecane,(S)-nicotine and sodium tungstate dihydrate.The samples were then characterized and analyzed by SEM,TEM,FTIR,UV-Vis,Nadsorption-desorption,XPS,ICP-OES,water contact angle and electronic circular dichroism.Moreover,studies were conducted to explore the catalytic performance of the samples for dihydroxylation of styrene.The results demonstrated that the chiral tungstic ionic liquid was successfully embedded in the mesoporous hollow spheres with a diameter of about 100 nm,a BET surface area of 20~54 m^(2)/g,and average pore diameter of 7.73~15.98 nm.Meanwhile,the spherical solids presented circular dichroism and could promote dihydroxylation of styrene leading the yield of product(R)-phenylethylene glycol to 89.6%with reaction time 3 h and still up to 87.0%after being used for 5 times when n(W)∶n(Si)=0.25∶0.75.It was speculated that tungstate chiral ionic liquid could guide the formation of mesoporous hollow silicon spheres since samples without tungstate ionic liquid was amorphous.

关 键 词：手性 离子液体 催化 介孔硅球 双羟化 催化技术 

分 类 号：TQ223.1[化学工程—有机化工] TQ426