均相与多相催化剂在CO_(2)环加成反应中的研究进展  

Research progress of homogeneous and heterogeneous catalysts in CO_(2) cycloaddition reactions

作　　者：李宁宁 刘轩博 张宇航 王雨佳 常涛 朱正 LI Ningning;LIU Xuanbo;ZHANG Yuhang;WANG Yujia;CHANG Tao;ZHU Zheng(Key Laboratory of CO_(2) Utilization of Handan City,College of Material Science and Engineering,Hebei University of Engineering,Handan 056038,China;Key Laboratory of Heterocyclic Compounds of Hebei Province,Handan College,Handan 056005,China)

机构地区：[1]河北工程大学材料科学与工程学院邯郸市CO_(2)催化转化重点实验室,河北邯郸056038 [2]河北省杂环化合物重点实验室,河北邯郸056005

出　　处：《燃料化学学报（中英文）》2024年第1期105-130,共26页Journal of Fuel Chemistry and Technology

基　　金：中央引导地方科技发展资金项目(226Z4304G);河北省自然科学基金(B2020402002,E2021402017)资助。

摘　　要：二氧化碳(CO_(2))是一种主要的人为温室气体,主要由化学、热电和钢铁工业以及运输等部门产生。大气层中CO_(2)浓度的增加是导致诸多环境问题的主要原因,如全球变暖、海平面上升和全球气温升高。然而,CO_(2)作为一种可再生、廉价和无毒的化学原料,可用来生产具有高附加值的化学品,进而降低碳浓度。五元环碳酸酯由于其优越的物理化学特性,如高沸点、高偶极矩和生物降解等性能而被广泛应用。由环氧化合物和CO_(2)合成环碳酸酯是迄今为止研究较多的方法。然而,由于CO_(2)的高热稳定性和动力学惰性,使其作为反应原料需要大量的能量投入,可能导致的结果是CO_(2)浓度是一个净增长过程。因此,利用CO_(2)作为C1构筑单元是一个长期的挑战。本工作基于CO_(2)固定反应机制,概述了各种类型的均相和多相催化剂在CO_(2)固定反应合成精细化学品环状碳酸酯中的研究进展,包括有机催化剂、离子液体、金属有机框架化合物、多孔有机聚合物等。目前,几乎所有类别催化剂均可以在室温和低压力下,以实验室规模成功地使用纯CO_(2)将其固定到末端环氧化合物上,对于非末端环氧化合物通过更高的温度和压力以实现相应转化。同时,分析了催化剂在多取代环氧化合物或生物衍生环氧化合物转化、低浓度CO_(2)转化和实现工业化三个方面所面临的挑战,并提出了未来相关研究努力的方向。Carbon dioxide(CO_(2))is a major anthropogenic greenhouse gas produced by chemical,thermoelectric and steel industries as well as transport sector.The increasing concentration of CO_(2) in atmosphere is responsible for plenty of environmental problems such as global warming,rising sea levels and increasing global temperatures.However,CO_(2) could consider as renewable,cheap and non-toxic chemical raw material,using CO_(2) to produce high value-added chemicals to reduce carbon concentrations is a highly desirable strategy.Five-membered cyclic carbonates have a wide range of applications due to their superior physicochemical properties such as high boiling point,high dipole moment and biodegradability.The synthesis of cyclic carbonates from epoxides and CO_(2) is by far the most approved method.Nevertheless,due to high thermal stability and kinetic inertness,it is necessary to activate CO_(2) as feedstock for organic synthesis with large energy,which may result in the release of more CO_(2) than is actually.Therefore,the use of CO_(2) as C1 building block is long-term challenged.This paper outlines the progress of research on various types of homogeneous and heterogeneous catalysts for CO_(2) fixation to generate cyclic carbonates,including organocatalysts,ionic liquids,metal-organic frameworks,and porous organic polymers.Almost all of these catalysts are currently available for the successful fixation of CO_(2) to terminal epoxides on laboratory scale using pure CO_(2) at ambient temperatures.For internal epoxides higher reaction conditions are usually required to achieve the desired conversion.It was analyzed three areas of present major challenges in catalyzing multi-substituted epoxides or bio-derived epoxides,diluted CO_(2) conversion and industrialization,and the directions for future research efforts on the subject were suggested.

关 键 词：CO_(2) 环氧化合物 催化剂 环加成反应 环碳酸酯 

分 类 号：O643.36[理学—物理化学]