State Key Laboratory of Clean and Efficient Utilization of Coal-based Energy, Taiyuan university of technology
School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology

Shanxi Tianji Coal Chemical Industry Group Co.Ltd

通过双氨基功能化离子液体与对苯二甲醛原位共价组装得到柔性聚合物（DP），并采用后合成修饰法将DP包覆于金属有机框架材料MIL-101（Cr）表面，构筑了一种核-壳型复合材料（MIL-101@DP）用于催化CO2和环氧氯丙烷（ECH）环加成反应。MIL-101@DP保留了MIL-101（Cr）高比表面积和高孔隙率的优点，并兼具亲核位点Cl−与Lewis酸性位点Cr3 + 。在Lewis酸碱位点协同作用下，MIL-101@DP可在常压、80 ℃、24 h且无助催化剂的条件下高效催化转化CO2和ECH反应（ECH转化率可达99%），且在循环使用四次后活性未出现明显下降。

A flexible polymer (DP) was prepared by in-situ covalent assembly of dual-amino-functionalized ionic liquids and terephthalaldehyde. A core-shell composite (MIL-101@DP) was constructed by coating DP on the surface of metal-organic frame material MIL-101 (Cr) by post-synthesis modification, and was applied to catalyze the cycloaddition reaction of CO2 and epichlorohydrin (ECH). MIL-101@DP retains the advantage of high specific surface area and high porosity of MIL-101 (Cr), and combines the nucleophilic site Cl− and Lewis acidic site Cr3 + . Under the synergistic interaction of Lewis acid sites and Lewis base sites, MIL-101@DP could efficiently catalyze activity the conversion of CO2 and ECH reaction (ECH conversion rate can reach 99%) at atmospheric pressure, 80 ℃, 24 h and without cocatalyst. The activity did not decrease significantly after four cycles.

国家自然科学基金面上基金 （22272125），榆林学院中国科学院洁净能源创新研究院联合基金（YLU-DNL Fund 2021021），武汉市科技局知识创新专项基础研究项目（2022020801010354）和山西浙大新材料与化工研究院项目（2022SXTD015）资助

胡凤群, 邱明月, 易群, 张鼎, 李向远, 李剑川, 史利娟, 段小川. 核壳型MOFs@离子液体复合材料的制备及其常压下催化CO2环加成反应性能探究[J]. 燃料化学学报（中英文）, 2023, 51(11): 1673-1682.

HU Feng-qun, QIU Ming-yue, YI Qun, ZHANG Ding, LI Xiang-yuan, LI Jian-chuan, SHI Li-juan, DUAN Xiao-chuan. Construction of core-shell MOFs@ionic liquid materials and their performance for CO2 cycloaddition reaction under atmospheric pressure[J]. Journal of Fuel Chemistry and Technology, 2023, 51(11): 1673-1682.