【作者】 袁慧；

【导师】 潘晓梅；

【作者基本信息】 东南大学 ， 化学工程与技术， 2020， 硕士

【摘要】 自工业革命以来,将二氧化碳进行捕集和化学固定,并且用于后续的资源利用获得化工产品是当前科学界研究的主题,以创造经济价值,提高资源利用率。CO₂与环氧化物生成环状碳酸酯（PC）的反应是最绿色的经济反应之一,环状碳酸酯作为有机合成中非常重要的化学产品,在化工生产方面具有广泛的用途。继科研工作者合成金属有机骨架材料（MOFs）之后,发现了一种更复杂的沸石咪唑酯骨架材料（ZIFs）,该材料由金属Zn或Co桥接咪唑环有机分子组成。由于其巨大的比表面积,极高的热稳定性,易于回收,结构多样以及可调节的性能,在催化等领域具有诱人的应用前景。当在温和条件下除去溶剂分子时,某些ZIFs可以在晶体结构内形成不饱和位点,以促进CO₂环氧化反应。离子液体是由阴、阳离子组成的一种熔融的盐,在常温常压下以液态形式存在。当卤素离子作为阴离子时,由于其具有很强亲核性而且易离去,在CO₂的环加成反应中具有促进环氧化合物开环的作用。本文分别通过共价键结合和溶剂热法,将吡啶基离子液体引入多种ZIFs中,合成负载型催化剂,首先用多种现代表征方法对它们的组成结构以及理化性质进行了分析,然后将其应用于CO₂与环氧丙烷（PO）的偶联反应,最后通过研究不同参数对结果的影响,探索最优的反应条件,得出结论如下:（1）制备了三种吡啶基离子液体:1-氨基乙基-吡啶溴盐、1-氨基乙基-2-甲基吡啶溴盐、1-氨基乙基-3-甲基吡啶溴盐,并通过形成新的化学键分别将它们接枝到ZIF-90骨架上,合成ZIF-90-IL-1,ZIF-90-IL-2和ZIF-90-IL-3三种催化剂。反应结果表明,在同一条件下,ZIF-90-IL-1催化效果最好,且在CO₂与多种环氧化合物的偶联反应中都表现出高活性。在90°C,25 bar的CO₂压力下反应8 h,PO的转化率为96.27%,PC的选择性为98.17%。（2）合成了ZIF-8,ZIF-67,ZIF-7,ZIF-9,并将其作为载体,通过溶剂热法,负载1-氨基乙基-吡啶溴盐,分别了合成催化剂ZIF-8-IL-1,ZIF-67-IL-1,ZIF-7-IL-1,ZIF-9-IL-1。其中,ZIF-8-IL-1表现出了最强的催化活性。在最佳反应条件下（120°C,20 bar,8 h,1.0 wt.%）,PO的转化率为96.73%,PC的选择性为99.08%。更多还原

【Abstract】 Since the industrial revolution,the capture and chemical fixation of carbon dioxide,and the subsequent use of CO₂ resources to obtain chemical products are the subject of current scientific research to create economic value and improve resource utilization.The reaction of CO₂ and epoxide to form cyclic carbonate（PC）is one of the greenest economic reactions.As a very important chemical product in organic synthesis,cyclic carbonate has a wide range of uses in chemical production.Following the synthesis of metal organic framework materials（MOFs）by scientific researchers,a more complex zeolite imidazolate framework material（ZIFs）was discovered,which was composed of metal Zn or Co bridged imidazole ring organic molecules.Due to its huge specific surface area,extremely high thermal stability,easy recycling,diverse structure and adjustable performance,it has attractive application prospects in the fields of catalysis and the like.When the solvent molecules are removed under mild conditions,some ZIFs can form unsaturated sites within the crystal structure to promote CO₂ epoxidation.Ionic liquid is a molten salt composed of anions and cations,which exists in liquid form at normal temperature and pressure.When halogen ions are used as anions,due to their strong nucleophilicity and easy to leave,they have the role of promoting the ring opening of epoxy compounds in the cycloaddition reaction of CO₂,and show significant catalytic activity in this reaction.In this paper,to synthesize supported catalysts,pyridyl ionic liquids were introduced into various ZIFs by covalent bonding and solvothermal methods.Firstly,their compositional structure and physicochemical properties were analyzed by various modern characterization methods.It is applied to the coupling reaction of CO₂ and propylene oxide（PO）.Finally,the effect of different conditions on the catalytic performance was investigated,and the optimal reaction conditions were explored.The results are as follows:（1）Three pyridyl ionic liquids were prepared:1-aminoethyl-pyridine bromide,1-aminoethyl-2-methylpyridine bromide,1-aminoethyl-3-methylpyridine bromide,and by forming new chemical bonds and grafting them to ZIF-90,three catalysts,ZIF-90-IL-1,ZIF-90-IL-2 and ZIF-90-IL-3,were synthesized.The reaction results showed that under the same conditions,ZIF-90-IL-1 had the best catalytic effect and showed high activity in the coupling reaction between CO₂ and various epoxy compounds.The reaction was carried out at 90°C and 20 bar for 8 hours,the conversion of PO was96.27%,and the selectivity of PC was 98.17%.（2）Synthesized four materials ZIF-8,ZIF-67,ZIF-7,ZIF-9 as carriers,and load 1-aminoethyl-pyridine bromide onto these four carriers by solvothermal method to synthesize the supported catalysts ZIF-8-IL-1,ZIF-67-IL-1,ZIF-7-IL-1,ZIF-9-IL-1.Among them,ZIF-8-IL-1 showed the strongest catalytic activity.Under the optimal reaction conditions（120°C,20 bar,8 h,1.0 wt.%）,The conversion of PO was 96.73%,and the selectivity of PC was 99.08%.更多还原