基于卟啉配体构筑的金属—有机框架的合成及催化性质研究

发布时间：2018-01-05 19:22

本文关键词：基于卟啉配体构筑的金属—有机框架的合成及催化性质研究　出处：《东北师范大学》2017年博士论文　论文类型：学位论文

【摘要】：金属-有机框架(MOFs)作为一类新兴的多孔材料在过去十几年发展迅速,并在众多领域有潜在的应用前景。将卟啉或金属卟啉引入MOFs中,可以制备出光电和催化性能优异的新材料。本论文以三种卟啉作为配体利用溶剂热方法自组装合成了四种MOFs。这四种MOFs有不同的结构和活性位点。我们依据每个化合物的特点,研究其对不同反应的催化性能,并探究其适用性和可循环性等。1.使用H_2tppp作为配体(H_2tppp=5,10,15,20-四(4-(3-(2-吡嗪基)吡唑基)苯基)卟啉),在溶剂热条件下成功得到了两个混价化合物[Cu(I)6I6(Cu(II)-tppp)]·2DMF(1)和[Ag(I)(NO3)0.5(Ag(II)-tppp)]·0.5NO3·DMF(2)。在化合物1中,每一个Cu(II)-tppp配体连接六个[Cu6I6]簇得到一个迷人的2D网络。化合物2中,毗邻的Ag(I)离子由Ag(II)-tppp连接形成一个1D链。研究了这两个化合物对于叠氮-炔环加成(AAC)反应和乙基苯氧化反应的催化性能。结果表明化合物1对这两个反应有着优异的催化活性并且可以循环使用。2.利用柔性八元羧酸卟啉H10L(H10L=5,10,15,20-四(4-(3,5-二羧基苯氧基)苯基)卟啉)合成了一个多孔的具有金红石(rtl)拓扑的MOF[Mn5L(H_2O)6·(DMA)2]·5DMA·4C2H5OH(3)。化合物3的框架中高的Mn(II)离子密度使其可以作为路易斯酸催化CO_2固定反应。我们分别在常压和高压条件下测试其催化性能。结果表明3对于CO_2与环氧化物的环加成反应有着较好的的催化活性,在20 atm下其转化频率(TOF)可以达到400 h-1。并且对于空间位阻不同的反应底物,3表现出尺寸选择性。3.利用混合配体H_2tipp和H_2bpdc(H_2tipp=5,10,15,20-四(4-咪唑基)苯基)卟啉,H_2bpdc=4,4'-联苯二甲酸)构筑了一个多孔的4重穿插的具有斜硅石(mog)拓扑的MOF[Cd3(tipp)(bpdc)2]·DMA·9H_2O(4)。框架中的Cd离子和羧基氧提供了丰富的路易斯酸和路易斯碱位点。化合物4可以高效异相催化醛的硅腈化反应和Knoevenagel缩合反应。不仅如此,4对催化这两个C-C键形成反应有着较好的可循环性和底物选择性。
[Abstract]:As a new kind of porous materials, metal-organic frameworks (MOFs) have been developing rapidly in the past decade and have potential applications in many fields. Porphyrins or metalloporphyrins are introduced into MOFs. In this paper, three porphyrins were used as ligands to synthesize four kinds of MOFs by solvothermal self-assembly. The four MOFs have different structures and active sites. We depend on the characteristics of each compound. The catalytic properties of H2tppp for different reactions were studied, and its applicability and circulability were investigated. 1. H2tppp was used as ligand. Two mixed valence compounds have been successfully obtained under solvothermal conditions by 20 Tetrazapylae 3-pyrazinyl) pyrazinyl) phenyl) porphyrins. [2)))] 路2DMF ~ (1)) and. [In compound 1, each of the Cu(II)-tppp ligands is linked to six. [Cu6I6] clusters get a fascinating 2D network. Compound 2. The adjacent Agni) ions are joined by Ag(II)-tppp to form a 1D chain. The effects of these two compounds on the azido-acetylene cycloaddition (AAC) have been studied. Catalytic properties of the reaction and the oxidation of ethylbenzene. The results show that compound 1 has excellent catalytic activity for these two reactions and can be reused. 2. Using flexible octa-carboxylic acid porphyrin H10L (. H10 L5. A porous MOF with rutile rtl topology was synthesized. [Mn5L(H_2O)6 路DMA2] 路5DMA 路4C2H _ 5OH _ (3). High MNO _ (II) in the frame of compound 3. The ionic density makes it possible to catalyze the CO_2 immobilization reaction with Lewis acid. The catalytic properties of the catalyst are tested at atmospheric pressure and high pressure respectively. The results show that 3 has a good effect on the cycloaddition reaction between CO_2 and epoxides. Better catalytic activity. The conversion frequency can reach 400h-1 at 20 atm, and the reaction substrate with different steric resistance can be obtained. (3) size selectivity. 3. Using the mixed ligands H _ 2tipp and H _ 2bpdche _ H _ 2tippa _ (5) 1010 ~ 1520 ~ (tetrazolidazolyl) phenyl) porphyrin. H2bpdc4) A porous MOF with a 4-fold intercalation with orthosilicate mog) has been constructed. [Cd3(tipp)(bpdc)2] 路DMA 路9H2O4). CD ion and carboxyl oxygen in the framework provide abundant Lewis acid and Lewis base sites. Compound 4 can efficiently catalyze the siliconitrile reaction and Knoevenagel condensation of aldehydes. Here. 4 has good cycle ability and substrate selectivity to catalyze the formation of these two C-C bonds.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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