摘要
利用羧基与金属Cr^(3+)的配位作用,将羧基咪唑离子液体1-丙酸-3-甲基咪唑氯原位组装于金属-有机框架材料MIL-101骨架结构中,制成了具有丰富Lewis酸、碱性活性位点的多相催化剂MIL-101-CFIL,并将其用于催化CO_2与环氧氯丙烷的环加成反应,考察了反应温度、CO_2压力对产物氯丙烯碳酸酯产率和选择性的影响。元素分析、XRD、SEM、N_2吸脱附等表征结果证明离子液体成功固载到MIL-101骨架中。催化剂中的Lewis酸、碱性两种活性位点对CO_2的环加成反应有良好的协同催化效应,从而在无溶剂、无助剂及温和的条件下高效催化转化CO_2。在最佳反应条件(50℃、0.5MPa CO_2、24h)下,产物氯丙烯碳酸酯的产率和选择性分别高达为98.5%和99.2%,反应后催化剂经过离心即可分离回收利用,重复使用4次后仍保持较高的反应活性。
The heterogeneous catalyst MIL-101-CFIL containing both Lewis acid and basic active sites was prepared by immobilizing the ionic liquid 1-propionic acid-3-methylimidazolium on metal-organic framework MIL-101 and using the coordination function of the carboxyl group with the metal Cr3+.The prepared catalyst was used for the cycloaddition of CO2 with epichlorohydrin,and the effects of reaction temperature and CO2 pressure on the yield and selectivity of chloropropene carbonate were investigated.The results of elemental analysis,XRD,SEM and N2 adsorption-desorption showed that the ionic liquids were successfully grafted on the support of MIL-101.It was found that the Lewis acid and alkaline active sites in the catalyst have a good synergistic catalytic effect on the cycloaddition reaction of CO2,thereby efficiently converting CO2 under solvent-free,additive-free and mild conditions.Under the optimal reaction conditions(50℃,0.5MPa CO2,24h),the yield and selectivity of the product chloropropene carbonate were up to 98.5%and 99.2%,respectively.After the reaction,the catalyst could be separated and recycled easily by centrifugation,and a high catalytic activity was maintained after being reused four times.
作者
李军
许少勃
刘婷婷
张奇日
谷莹秋
史利娟
LI JUN;XU Shao-bo;LIU Ting-ting;ZHANG Qi-ri;Gu Ying-qiou;SHI Li-juan(Department of Applied Chemistry,Yuncheng University,Yuncheng 044000,China;Key Laboratory of Coal Science and Technology,Ministry of Education and Shanxi Province,Taiyuan University of Technology,Taiyuan 030024,China;School of Chemistry and Materials Science,Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials,Jiangsu Normal University,Xuzhou 221116,China)
出处
《天然气化工—C1化学与化工》
CAS
CSCD
北大核心
2018年第4期35-40,68,共7页
Natural Gas Chemical Industry
基金
国家自然科学基金青年基金(21403151)
山西省应用基础研究项目青年科技研究基金资助项目(2016021045)
江苏省自然科学基金(BK20170 232)
运城学院科研基金(YQ-2017008)。
关键词
离子液体
金属有机骨架材料
二氧化碳
环加成
氯丙烯碳酸酯
温和条件
ionic liquids
metal organic frameworks
carbon dioxide
cycloaddition
chloropropene carbonate
mild condition
