BTB和含氮羧酸配体构筑的金属有机骨架材料的合成及其性能研究

发布时间：2018-12-31 09:48

【摘要】：金属有机骨架材料(MOFs)作为一类迷人的多孔晶态材料,由于结构和功能具有可调控性,成为化学和材料化学领域研究的一个热点。它们具有特殊的结构特点,比如比表面积大,孔隙率高,孔尺寸可调等等,使其表现出多种多样潜在的应用,如在气体存储和分离、传感、催化、药物输送等方面。当前,合成MOFs材料的中心金属离子主要为过渡金属离子和稀土金属离子,有机配体一般为羧酸配体和氮唑配体。本文中选用1,3,5-三(4-羧基苯基)苯(H3BTB)和稀土金属离子合成一种MOFs材料,另外,选用5-羧酸苯并三氮唑(H_2btca)与过渡金属离子合成一种MOFs材料,并对他们的性质进行了研究。本论文共分四部分:第一章引言部分为MOFs材料的简介,重点介绍MOFs材料在催化、荧光、磁性方面的研究应用以及本论文选题意义和目前的研究状况。第二章描述了利用有机配体1,3,5-三(4-羧基苯基)苯(H3BTB)和金属盐硝酸钇,在溶剂热条件下,合成了一种具有18连接网络结构和gea拓扑结构的MOFs材料,(DMA)_2[Y_9(μ_3-OH)_8(μ_2-OH)_3(BTB)_6]n·(solv)x(1),1,3,5-三(4-羧基苯基)苯具有共轭π体系,自身具有良好的荧光性质,而由这类配体构筑的MOFs材料通常也有好的荧光性能,因此,研究其荧光性能。第三章描述了利用有机配体5-羧酸苯并三氮唑(H_2btca)和金属盐乙酸锰,在溶剂热条件下,合成了一个迷人的含有四方形孔洞的MOFs材料:Mn6(btca)4(μ3-OH)2·(EtOH)2·4H_2O(2);接着在相同条件下,又引入第二种配体4,4′-联吡啶(4,4′-bpy),合成另一个迷人的含有四方形孔洞的MOFs材料Mn_6(btca)_4(μ3-OH)_2·(EtOH)_2·bpy·DMF(3)。由于Mn-MOF(2)和Mn-MOF(3)具有开放的活性位点,用作Lewis酸催化剂催化Cyanosilylation reaction,来研究其催化性能,Mn-MOF(3)催化苯甲醛和三甲基氰硅烷的Cyanosilylation reaction,其转化率低于Mn-MOF(2),由于其孔道内含有客体分子,影响反应底物进入孔道,只能在Mn-MOF(3)的表面反应。同时也对Mn-MOF(2)的磁性做了研究。第四章对本论文中的三种MOFs材料的应用进行总结,为今后合成具有多功能MOFs材料提供了新的策略。
[Abstract]:As a kind of attractive porous crystalline material, metal-organic skeleton material (MOFs) has become a hotspot in the field of chemistry and material chemistry because of its controllable structure and function. They have special structural characteristics, such as large specific surface area, high porosity, adjustable pore size and so on, which make them show a variety of potential applications, such as gas storage and separation, sensing, catalysis, drug transportation and so on. At present, transition metal ions and rare earth metal ions are the main metal ions in the synthesis of MOFs, while the organic ligands are usually carboxylic acid ligands and azazole ligands. In this paper, a kind of MOFs material was synthesized by using 1 ~ (3) C ~ (3 +) -tris (4-carboxyphenyl) benzene (H3BTB) and rare earth metal ions. In addition, a kind of MOFs material was synthesized by using 5-carboxylic acid benzo triazole (H_2btca) and transition metal ions. Their properties are also studied. This paper is divided into four parts: the first chapter is the introduction of MOFs materials, focusing on the catalytic, fluorescent and magnetic applications of MOFs materials, as well as the significance of this paper and the current research situation. In chapter 2, we describe the synthesis of a kind of MOFs material with 18-connected network structure and gea topology under solvothermal conditions using organic ligands 1 ~ (3) O _ (3) -tris (4-carboxyphenyl) benzene (H3BTB) and metal salt yttrium nitrate. (DMA) _ 2 [Ys _ 9 (渭 _ 3-OH) _ 8 (渭 _ 2-OH) _ 3 (BTB) _ 6] n (solv) x (_ 1), 1C _ 3N _ 5- tris (4-carboxyl phenyl) benzene has conjugated 蟺 system and has good fluorescence properties. The MOFs materials constructed by this kind of ligands usually have good fluorescence properties, therefore, their fluorescence properties are studied. Chapter 3 describes the use of organic ligand 5-carboxylic acid benzotriazole (H_2btca) and metal salt manganese acetate under solvothermal conditions. A fascinating MOFs material containing square holes was synthesized: Mn6 (btca) _ 4 (渭 3-OH) _ 2 (EtOH) _ 2 4H_2O (2); Then, under the same conditions, a second ligand, 4zapyridine (4PY), was introduced. Another fascinating MOFs material, Mn_6 (btca) _ 4 (渭 3-OH) _ 2 (EtOH) _ 2 bpy DMF (_ 3, was synthesized. Because Mn-MOF (2) and Mn-MOF (3) have open active sites, they can be used as Lewis acid catalyst to study the catalytic activity of Cyanosilylation reaction,. Mn-MOF (3) catalyzes the Cyanosilylation reaction, of benzaldehyde and trimethylcyanosilane. The conversion rate of Mn-MOF (2) is lower than that of Mn-MOF (2). Due to the presence of guest molecules in the pore channel, the reaction substrate can only react on the surface of Mn-MOF (3) because of its influence on the entry of the substrate into the pore channel. The magnetic properties of Mn-MOF (2) were also studied. In chapter 4, the application of three kinds of MOFs materials in this thesis is summarized, which provides a new strategy for the synthesis of multifunctional MOFs 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】：O641.4

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