功能性金属有机骨架材料催化串联反应的研究

发布时间：2019-04-19 08:53

【摘要】：近年来,金属有机骨架材料(MOFs)作为催化剂在合成化学领域已经有显著发展。MOFs在所有材料中具有最高孔隙率,并且它们的孔径大小,形状,维度可以被精细调控。MOFs设计上的多样性为其在催化领域的应用提供了明显优势。MOFs的活性位点可以存在于金属或金属簇节点、有机配体上,也可以在MOFs的孔或空腔内引入活性客体。金属有机骨架材料可以通过化学方法设计成同时具有多种催化活性位点的功能性材料,这使得一种催化剂催化多步反应成为可能。第一章,我们对金属有机骨架材料的结构和其应用性能进行了简要介绍,总结了金属有机骨架材料从诞生到快速发展的研究成果,以及功能性金属有机骨架材料在催化串联反应方面的现阶段研究状况。第二章,介绍了金属有机骨架 MIL-101 (Al,Cr, Fe)和 NH2-MIL-101 (A1,Cr, Fe)系列材料的合成、活化方法,并对它们进行化学表征。XRD和IR表征证明两个系列金属有机骨架材料已经成功合成,SEM表征可以清晰的比较出NH2-MIL-101 (M=Al,Cr,Fe)三种晶体结晶度的高低。第三章,将合成的NH2-MIL-101 (Al,Cr,Fe)应用到催化串联反应:脱缩醛—诺文格尔缩合串联反应,它们均展现出良好的催化效果。在最优的反应条件下,比较了 NH2-MIL-101 (M = Al,Cr, Fe)催化该串联反应的催化效果。通过相关资料分析,证明了晶体结晶度是影响它们催化效果差异的重要原因。第四章,利用过量浸渍法将贵金属Pd纳米粒子引入到NH2-MIL-101 (A1,Cr,Fe)孔洞内部,合成了具有Pd纳米粒子活性中心的功能性MOFs材料Pd@NH2-MIL-101 (Al,Cr, Fe)。对其进行的化学表征表明,Pd纳米粒子成功引入到MOFs孔洞内部且负载过程没有破坏MOFs主体框架和功能位点。第五章,将合成的Pd@NH2-MIL-101 (Al,Cr,Fe)应用到催化串联反应:醇液相氧化—诺文格尔缩合反应,它们均展现出良好的催化效果。在最优的反应条件下,比较了 Pd@NH2-MIL-101 (M = Al,Cr,Fe)在催化该串联反应的催化效果。通过相关资料分析,证明了纳米粒子负载的均匀程度和离子间的协同效应是影响它们催化效果差异的重要原因。第六章,对所做的工作进行总结,为今后金属有骨架材料在催化串联反应方面的研究提供借鉴。
[Abstract]:In recent years, (MOFs), a metal-organic framework material, has been developed significantly as a catalyst in synthetic chemistry. MOFs have the highest porosity in all materials, and their pore sizes and shapes. Dimensions can be fine regulated. The diversity in design of MOFs provides a significant advantage for their applications in the field of catalysis. The active sites of MOFs can exist in metal or metal cluster nodes, organic ligands, and so on. Active guest can also be introduced into the hole or cavity of MOFs. Organometallic framework materials can be chemically designed into functional materials with multiple catalytic activity sites at the same time, which makes it possible for a catalyst to catalyze multi-step reactions. In the first chapter, we briefly introduce the structure and application properties of metal-organic framework materials, and summarize the research results from birth to rapid development of metal-organic framework materials. And the present research status of functional organometallic framework materials in catalytic series reaction. In the second chapter, the synthesis and activation of organometallic framework MIL-101 (Al,Cr, Fe) and NH2-MIL-101 (A1, Cr, Fe) series materials are introduced. X-ray diffraction (XRD) and IR showed that two series of organometallic skeleton materials had been successfully synthesized. The crystallinity of NH2-MIL-101 (Mal Al, Cr, Fe) crystals could be clearly compared by SEM characterization. In the third chapter, the synthesized NH2-MIL-101 (Al,Cr,Fe) was applied to the catalytic series reaction: de-acetal-Novinger condensation tandem reaction, which showed good catalytic effect. Under the optimum reaction conditions, the catalytic effect of NH2-MIL-101 (M = Al,Cr, Fe) on the series reaction was compared. Through the analysis of related data, it is proved that the crystallinity of crystals is the important reason that affects the difference of catalytic effect between them. In chapter 4, precious metal Pd nanoparticles were introduced into NH2-MIL-101 (A1, Cr, Fe) pores by excessive impregnation, and functional MOFs materials Pd@NH2-MIL-101 (Al,Cr, Fe).) with active centers of Pd nanoparticles were synthesized. The chemical characterization showed that the Pd nanoparticles were successfully introduced into the MOFs pores and the main frame and functional sites of MOFs were not destroyed during the loading process. In the fifth chapter, the synthesized Pd@NH2-MIL-101 (Al,Cr,Fe) is applied to the catalytic series reaction: alcohol liquid phase oxidation-Novinger condensation reaction, and they all show good catalytic effect. Under the optimum reaction conditions, the catalytic effect of Pd@NH2-MIL-101 (M = Al,Cr,Fe) on the series reaction was compared. Through the analysis of related data, it is proved that the uniformity of nanoparticles loading and the synergetic effect between ions are the important reasons that affect the difference of catalytic effect. Chapter 6 summarizes the work done in order to provide reference for the research on catalytic series reaction of metal-framework materials in the future.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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