异金属有机骨架材料的设计合成及其潜在应用性能的探究

发布时间：2018-03-19 20:43

本文选题：异金属有机骨架化合物　切入点：原位配体合成　出处：《青岛科技大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属有机骨架材料(Metal-Organic Frameworks,MOFs)以其丰富的结构类型和在气体吸附与分离、催化、荧光探针、传感、以及离子交换等领域具有非常巨大的潜在应用价值,吸引了越来越多的科研工作者的关注与研究。定向的设计与合成具有特殊结构,特定功能的金属有机骨架化合物一直是材料化学里的热点问题。目前为止,已有大量的金属有机骨架化合物被成功地制备。但是对于其合理的设计,合成方法的优化,以及影响因素的分析仍然需要不断的探索。本文从晶体工程学的原理出发,以金属有机骨架化合物的功能性为导向,致力于异金属有机骨架化合物(Heterometallic Metal-Organic Frameworks,HMOFs)的设计与合成。并对异金属有机骨架化合物的原料选择,合成环境,合成方法等一系列问题进行了系统的研究。最终我们制备了几种异金属有机骨架化合物并对其进行了结构分析与性能表征。本论文的研究成果主要包括以下方面:1.运用配体原位合成的方法,通过精心选择含有S-S键的双官能团配体6,6'-二硫代二烟酸和金属离子In~(3+)、Cu~+,在溶剂热体系中通过S-S键的断裂键断裂原位生成多功能有机配体,并成功制备了一个具有阳离子骨架的三维异金属有机骨架化合物{[(CH_3)_2NH_2]InCu_4L_4·xS}n(BUT-52)(L=6-甲基吡啶-3-羧酸)。其具有非常罕见的硫原子装饰的哑铃型笼腔结构。通过一系列的实验证明,该材料具有良好的气体吸附/分离性能性能。对天然气CH_4中的主要混合成分C_2H_2,C_2H_4,C_2H_6具有良好的吸附分离能力;同时,基于BUT-52结构的硫原子和重金属离子Hg~(2+)等具有很强的结合能力,BUT-52表现出从较低浓度的甲醇溶液中响应并吸附Hg~(2+)的能力。同时因为BUT-52的阴离子骨架结构,使其对阳离子的染料也具有很好的吸附效果。2.在溶剂热条件下,我们选择一个富含氮原子的有机配体2,6-双[3-(吡嗪-2-基)-1,2,4-三唑]吡啶(H_2L),通过反应时间、反应温度和PH值等条件的调控,得到一个具有一维链状结构的配位聚合物[FeIIL(H_2O)]·2H_2O(配合物1),通过研究发现,配合物1具有出色的耐酸碱性质和热稳定性,并且通过溶剂介导的方法,将配合物1的晶体做为模板,在叠氮化钠饱和的甲醇溶液中重新自组装,成功制备出一个异金属的[2×2]网格结构配位化合物[Fe III_2Na_2L4(H_2O)_4]·8H_2O(配合物2)。该过程实现了由一维单金属链到[2×2]异金属网格结构的单晶转化。配合物1和2在磁性及电化学方面具有潜在的应用价值,值得进一步探索。3.首先我们通过软硬酸碱理论的指导,合理的选择配体和金属源设计合成出一个6连接稀土笼次级结构单元的二维层状单金属有机骨架化合物(化合物3)和一个具有12连接稀土笼次级结构单元的三维的单金属有机骨架化合物(化合物4)。并对其进行了结构分析和一系列的表征。随后我们对具有开放性螯合位点的三维单金属有机骨架化合物4的骨架结构进行二次金属化得到具有开放性金属位点的异金属有机骨架化合物,然后我们对该HMOFs在有机催化方面的性质进行了探索。我们发现被Pd~(2+)金属化后的化合物4对环己烯酮脱氢生成苯酚具有一定的催化效果。
[Abstract]:Metal organic frameworks (Metal-Organic, Frameworks, MOFs) with its rich structure type and in gas adsorption and separation, catalysis, sensing, fluorescence probe, has great potential application value in the field and ion exchange, has attracted more and more attention and research research work. Author oriented design and synthesis with special structure metal organic frameworks, the specific function is always a hot topic in material chemistry. So far, there has been a large number of metal organic framework compound was prepared successfully. But for its reasonable design, optimization and synthesis method, and analyzing the influencing factors still need continuous exploration. Based on the principle of crystal engineering, with functional metal organic frameworks oriented, committed to different metal organic frameworks (Heterometallic, Metal-Organic Frameworks, HMOFs) The design and synthesis of metal organic frameworks. And compound material selection, synthesis environment, studied a series of problems. Finally we made synthetic method of several different metal organic frameworks prepared and carried on the structure analysis and characterization. The research results of this thesis mainly includes the following aspects: 1. by using the method of in situ synthesis of ligand, through careful selection of bifunctional ligand 6,6'- two thio two nicotinic acid and metal ions In~ containing S-S bonds (3+), Cu~+, by in situ S-S bond bond cleavage fracture in solvothermal system generated multifunctional organic ligands, and prepared with a cationic skeleton 3D ISO metal organic frameworks (CH_3) {[_2NH_2]InCu_4L_4 - xS}n (BUT-52 (L=6-) -3- methyl pyridine carboxylic acid). The dumbbell shaped cavity structure with its cage rare sulfur atom decoration. Through a series of real The results show that the material has the properties of good gas adsorption / separation. C_2H_4 on the main components of natural gas mixing C_2H_2, CH_4, C_2H_6 has excellent adsorption separation; at the same time, sulfur atoms and heavy metal ions of Hg~ based on the structure of BUT-52 (2+) has a strong binding capacity, BUT-52 showed a response from the methanol solution of low concentration and the adsorption of Hg~ (2+). At the same time because of the ability of anionic framework structure of BUT-52, the cationic dye.2. has good adsorption effect under solvothermal conditions, we select a nitrogen rich organic ligand 2,6- double [3- (-2- based pyrazine) -1,2,4- three] pyridine (H_2L), the reaction time, reaction temperature and pH regulation conditions, obtained a 1D chain coordination polymer [FeIIL (H_2O)] - 2H_2O (complex 1), the study found that complex 1 has excellent resistance to The acid-base properties and thermal stability, and through the method of solvent mediated, the crystal of complex 1 as a template in the methanol solution of sodium azide saturated re self assembly, successfully prepared a heterometal [2 * 2] grid structure of coordination compounds [Fe III_2Na_2L4 (H_2O) _4] and 8H_2O (with the 2). The process is achieved by one-dimensional metal chain to single crystal [2 * 2] heterometallic lattice structure transformation. Complexes 1 and 2 in magnetism and electrochemistry has potential application value, worthy of further exploration of.3. we HSAB theory, design selection of ligands and metal source synthesis a 6 rare earth connection cage secondary structure unit of single layered metal organic frameworks (compound 3) and a 12 connection with rare earth cage secondary structure unit of three-dimensional single metal organic frameworks (compound 4) and its. The structural analysis and a series of characterization. The three-dimensional metal organic framework is an open frame structure 4 chelating sites for two times by different metal metal organic frameworks with open metal sites, then we on the HMOFs in organic catalytic properties were investigated. We found that Pd~ (2+) compound metal after 4 on cyclohexene dehydrogenation of phenol has a catalytic effect.

【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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