石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (11): 67-75.

• 催化剂 • 上一篇    下一篇

复合型催化剂MIL-101@PIL催化CO2环加成反应

李云肸,刘少青,徐爱浩,董丽辉,范闽光   

  1. 广西大学化学化工学院,广西石化资源加工及过程强化技术重点实验室
  • 收稿日期:2023-06-06 修回日期:2023-07-18 出版日期:2023-11-12 发布日期:2023-10-29
  • 通讯作者: 范闽光 E-mail:fanmg@gxu.edu.cn
  • 基金资助:
    金属固体材料/离子液体/二氧化碳环加成反应/机理研究;氮杂环离子液体嫁接金属有机骨架的构筑及其环加成反应性能

CO2 CYCLOADDITION REACTION CATALYZED BY COMPOSITE CATALYSTS MIL-101@PIL


  • Received:2023-06-06 Revised:2023-07-18 Online:2023-11-12 Published:2023-10-29

摘要: 针对CO2与环氧化物反应制备环碳酸盐需要高性能、低成本、易于回收的催化剂,制备了一种基于金属有机框架(MOF)的非均相催化剂(MIL-101@PIL)用于催化CO2转化为环碳酸酯。首先采用水热法制备MIL-101-Cr,然后在其孔道中负载具有较大分子体积的双季鏻盐离子液体1,4-双三苯基膦基丁烷溴盐。通过一系列对比试验考察,结果表明,MIL-101@PIL催化剂在无溶剂和助催化剂的情况下,具有较高的催化环加成反应生成环碳酸酯的活性。以合成碳酸丙烯酯为例,在优化条件下(MIL-101@PIL 80 mg,CO2压力1.4 MPa,环氧丙烷17 mmol,反应温度90 ℃,反应时间3 h),可获得较高的碳酸丙烯酯收率(95%)和选择性(99%),MIL-101@PIL催化剂较高的催化活性主要是由于配位不饱和Cr与Br阴离子之间具有协同催化作用。基于此,提出了MIL-101@PIL催化剂催化环加成反应的可能机理。

关键词: 金属有机框架, 离子液体, 环碳酸酯, 二氧化碳, 环加成

Abstract: The reaction of CO2 with epoxides to form cyclic carbonates requires a catalyst with high-performance, low-cost and easy recovery. A metal-organic frameworks (MOFs)-based heterogeneous catalyst (MIL-101@PIL) was prepared for catalytic conversion of CO2 to cyclic carbonates. Firstly, the MOF precursor MIL-101-Cr was prepared by hydrothermal synthesis, and then biquaternary phosphonium ionic liquid (1,4-bis-triphenylphosphonium butane bromide) with large molecular volume was loaded into its pore channel to form the catalyst MIL-101@PIL. A series of comparative experiments showed that the catalyst MIL-101@PIL had high activity in the synthesis of cyclocarbonate by cycloaddition reaction without solvent and co-catalyst. Under the optimum conditions (MIL-101@PIL mass of80 mg, CO2 pressure of 1.4 MPa,propylene oxide amount of 17 mmol, reaction temperature of 90 ℃, reaction time of 3 h), higher yield (95%) and selectivity (99%) were obtained. The results showed that the catalyst (MIL-101@PIL) had high catalytic activity, which was mainly due to the synergistic catalysis between the coordination unsaturated Cr sites and the Br anions. Based on this, a possible mechanism of cycloaddition reaction catalyzed by catalyst MIL-101@PIL was proposed.

Key words: metal-organic frameworks, ionic liquids, cyclic carbonates, carbon dioxide, cycloaddition