Lewis酸功能化介孔氧化硅限域柔性离子液聚合物协同催化CO2与环氧化合物环加成反应

doi:10.1016/S1872-2067(19)63340-1

催化学报 ›› 2019, Vol. 40 ›› Issue (12): 1874-1883.DOI: 10.1016/S1872-2067(19)63340-1

Lewis酸功能化介孔氧化硅限域柔性离子液聚合物协同催化CO₂与环氧化合物环加成反应

关茹群, 张晓明, 常芳芳, 薛楠, 杨恒权

山西大学化学化工学院, 山西太原 030006

收稿日期:2019-02-05 修回日期:2019-03-25 出版日期:2019-12-18 发布日期:2019-09-21
通讯作者: 张晓明, 杨恒权
基金资助:
山西省青年科技研究基金（2016021034）；山西大学人才事业启动经费（RSC723）.

Incorporation of flexible ionic polymers into a Lewis acid-functionalized mesoporous silica for cooperative conversion of CO₂ to cyclic carbonates

Ruqun Guan, Xiaoming Zhang, Fangfang Chang, Nan Xue, Hengquan Yang

School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China

Received:2019-02-05 Revised:2019-03-25 Online:2019-12-18 Published:2019-09-21
Supported by:
This work was supported by the National Natural Science Foundation of China (201573136, 21603128, U1510105), the Natural Science Foundation for Young Scientists of Shanxi Province (2016021034), and the Scientific Research Start-up Funds of Shanxi University (RSC723).

摘要/Abstract

摘要： 二氧化碳与环氧化物通过环加成制备环状碳酸酯是一个典型的“原子经济”和“绿色化学”反应，也是二氧化碳化学法利用最为有效的途径之一.离子液体催化剂因其独特的物理化学性质及催化活性，是该反应最常见和最有效的催化剂类型之一.然而，由于该反应为双组分协同作用机制，在催化反应过程中，通常要加入路易斯酸作为助催化剂来进攻环氧化合物上的氧原子，促进开环反应.因此，设计合成双组分在空间上能够相互接近的催化剂对促进协同效应，获得高活性催化剂至关重要.
本文利用介孔氧化硅材料表面易修饰、比表面积高和孔道易引入客体单元的特性，首先以阳离子表面活性剂CTAB为模板，通过预缩聚的策略将磺酸根基团引入到孔道表面，与ZnBr₂进行离子交换后，得到Lewis酸功能化的介孔氧化硅材料.然后，通过浸渍和热引发自由基聚合的方法将咪唑基线性离子液聚合物引入到材料孔道内，得到孔道限域离子液柔性聚合物和表面镶嵌Lewis酸单元的双组分催化剂.由于介孔孔道的空间限域作用和柔性聚合物的半“自由”性，在纳米尺度空间内可增强两种活性组分间的协同催化性能.在环氧丙烷的环加成反应中（110℃和2MPa CO₂条件下），所制备的双组分催化剂（转化率和选择性>99%）表现出优于单组分催化剂（转化率分别为4.5%和80%）和单组分催化剂混合物（转化率83%）的反应活性.同时，在相同反应条件下，向Lewis酸功能化氧化硅材料中后加入聚合离子液的反应体系转化率为96%，相较原位引入聚合离子液的方法仍有差距，这主要是由于离子液聚合物不能完全进入到孔道与Lewis酸中心接触造成的.因此，所制备的双组分催化剂的优异性能可能与增强的协同催化能力相关.由于聚合物链的缠绕作用和介孔孔道的限域作用，该双组分催化剂也具有较好的循环使用性能，循环使用4次后仍能得到85%的转化率.该研究进一步揭示了利用纳米孔限域空间可促进多组分位点协同催化，可能拓展至其它协同型催化剂的制备与应用.

关键词: 介孔氧化硅, 柔性离子液聚合物, 协同效应, 二氧化碳转化, 多相催化

Abstract: A rational integration of multiple reactive centers into a combined unit to facilitate their cooperative effects is a smart approach for accelerating the catalytic activity. Here, to achieve this goal, linear imidazolium-based ionic polymers were confined into the nanopores of mesoporous silica nanospheres anchored with homogeneously distributed zinc salts. Owing to the flexible character and the reinforced cooperative effects of the ionic liquid (nucleophile) and zinc species (Lewis acid) in the confined mesoporous structure, the resultant composite exhibited dramatically improved catalytic performance in the cycloaddition of CO₂ with epoxides to form cyclic carbonates. This was in contrast to that observed for the individual catalytic components. Moreover, such a solid catalyst could be easily recovered and reused four times without a significant loss of activity.

Key words: Mesoporous silica, Flexible ionic polymer, Cooperative effects, CO₂ utilization, Heterogeneous catalysis

关茹群, 张晓明, 常芳芳, 薛楠, 杨恒权. Lewis酸功能化介孔氧化硅限域柔性离子液聚合物协同催化CO₂与环氧化合物环加成反应[J]. 催化学报, 2019, 40(12): 1874-1883.

Ruqun Guan, Xiaoming Zhang, Fangfang Chang, Nan Xue, Hengquan Yang. Incorporation of flexible ionic polymers into a Lewis acid-functionalized mesoporous silica for cooperative conversion of CO₂ to cyclic carbonates[J]. Chinese Journal of Catalysis, 2019, 40(12): 1874-1883.

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Lewis酸功能化介孔氧化硅限域柔性离子液聚合物协同催化CO₂与环氧化合物环加成反应

Incorporation of flexible ionic polymers into a Lewis acid-functionalized mesoporous silica for cooperative conversion of CO₂ to cyclic carbonates

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