新型金属—有机骨架材料的设计合成及荧光、吸附性质研究

发布时间：2018-06-21 21:04

本文选题：有机配体 + 金属-有机骨架　；参考：《吉林大学》2017年硕士论文

【摘要】：在过去的二十年中,金属-有机骨架(Metal-organic frameworks,MOFs)材料已经成为化学家、物理学家以及材料科学家广泛研究的热点之一。金属-有机骨架材料主要是通过金属或金属簇与多齿有机配体自组装形成的一种高度结晶的无机-有机杂化材料。与传统的无机沸石和多孔碳相比,金属-有机骨架材料具有更优越的性能,比如:高的比表面积,孔道尺寸可调控,骨架易于修饰等,这使得该材料在荧光传感、储能、吸附分离、磁性、催化、药物释放等方面均展现出良好的应用价值。本论文中我们设计合成了两种新颖的有机配体,利用这两种配体分别与镧系元素和过渡金属铜元素在溶剂热条件下合成了一系列新型的MOFs材料,并对这些材料的结构与性质做了详细的表征,主要结果如下:1.基于1,2,3-三氮唑三羧酸配体的稀土金属-有机骨架材料对金属离子和硝基化合物的荧光传感:利用铜催化的叠氮化物-炔烃环加成(Cu AAC)反应合成了一个含有1,2,3-三氮唑的非对称三羧酸配体5-[4-(4-羧基-苯基)-[1,2,3]三唑-1-基]-间苯二甲酸(H3TAIP),在溶剂热条件下,H_3TAIP配体与稀土元素铽、镧、铕自组装形成了三例具有新颖三维结构的金属-有机骨架材料:[Tb(TAIP)(DMF)_2](化合物1),[La(TAIP)(DMF)_2]?(DMF)_(0.5)(化合物2)和[Eu(TAIP)(DMF)_2](化合物3)。单晶X-射线衍射分析表明这三个化合物具有相同的结构,均为镧系双核金属簇与TAIP3-配体形成的三维网状结构。它们结晶于单斜晶系C2/c空间群,简化后拓扑的顶点符号为(4~2?6)_2(4~4?6~2?8~7?10~2)。我们研究了三种化合物的荧光性质,测试结果表明化合物1-3均具有发光性质,且化合物1的发光强度明显高于化合物2、3,因此我们将化合物1用于对金属离子和硝基化合物的荧光传感,发现化合物1对4-硝基苯酚(4-NP)和三价铁离子Fe~(3+)均表现出了良好的选择性检测能力,是一种潜在的化学荧光传感材料。2.基于T形吡啶二羧酸配体的金属-有机骨架材料的合成及其对气体吸附性能的研究:利用Suzuki偶联反应合成了一个新型的T形吡啶二羧酸配体4?-(吡啶-4-基)-[1,1?-联苯]-3,5-二羧酸(H_2PBPD)。在溶剂热条件下,H_2PBPD配体与铜离子自组装形成了一例新颖的三维金属-有机骨架多孔材料[Cu(PBPD)(DMF)_2(H_2O)_3](化合物4)。单晶X-射线衍射分析表明该化合物结晶于六方晶系R-3空间群,是一种3,6连接的三维结构,简化后拓扑的顶点符号为(4~2?6)_2(4~4?6~2?8~6?10~3)。稳定性测试表明,化合物4在不同有机溶剂中浸泡两个月以及在空气氛围中250 oC煅烧半小时均能够保持原有的晶体结构。77 K氮气吸附-脱附测试表明,该化合物具有微孔特征,其BET比表面积为1682 m~2g~(-1)。另外,该化合物在273 K常压下对下甲烷和二氧化碳的吸附量分别为45 cm~3g~(-1)和114 cm~3 g~(-1)。最后,对化合物4做了二氧化碳循环吸附能力的测试,测试结果表明化合物4经过10次循环后吸附能力没有下降,并且保持了原有结构。以上实验结果表明该类配体在制备高稳定和高吸附性能的MOFs材料方面具有一定的价值。
[Abstract]:In the past twenty years, Metal-organic frameworks (MOFs) has become one of the hotspots of extensive research by chemists, physicists and material scientists. The metal organic skeleton material is a highly crystalline inorganic organic heterozygosity formed by the self-assembly of metal or metal clusters with multi tooth organic ligands. Compared with the traditional inorganic zeolite and porous carbon, the metal organic skeleton materials have superior properties, such as high specific surface area, the pore size can be controlled and the skeleton is easy to modify. This makes the material have good application value in the fields of fluorescence sensing, energy storage, adsorption and separation, magnetism, catalysis, drug release and so on. In this paper, two novel organic ligands were designed and synthesized. A series of new MOFs materials were synthesized with the two ligands and the lanthanide elements and transition metal copper elements respectively under the solvent heat condition. The structure and properties of these materials were characterized in detail. The main results are as follows: 1. based on the ligand of 1,2,3- three azoles three carboxylic acid ligands The fluorescence sensing of metal ions and nitro compounds by rare earth metal organic skeleton materials: a asymmetric three carboxylic acid ligand, 5-[4- (4- carboxy phenyl) -[1,2,3] three azoles -1- based -1- based -1- two formic acid (H3TAIP), is synthesized by the reaction of azide alkyne cycloaddition (Cu AAC) catalyzed by copper catalyzed reaction of azidazole and alkynes (1,2,3-). In solvent thermal condition, H_3 TAIP ligands and Rare Earth Terbium, lanthanum and europium have formed three metal organic skeleton materials with novel three-dimensional structure: [Tb (TAIP) (DMF) _2] (compound 1), [La (TAIP) (DMF) _2]? (0.5) (compound 2) and [Eu (TAIP) (3). Single crystal diffraction analysis shows that these three compounds have the same structure, all lanthanum It is a three-dimensional network structure formed by the binuclear metal clusters and TAIP3- ligands. They crystallize in the monoclinic C2/c space group. The vertex symbol of the simplified topology is (4~2? 6) _2 (4~4? 6~2? 8~7? 10~2). The fluorescence properties of the three compounds are studied. The test results show that the compounds 1-3 have luminescent properties, and the luminescence intensity of compound 1 is significantly higher. In compound 2,3, we use compound 1 for the fluorescence sensing of metal ions and nitro compounds. It is found that compound 1 shows good selectivity for 4- nitrophenol (4-NP) and trivalent iron ion Fe~ (3+). It is a potential chemical fluorescence sensing material.2. based on the T - shaped pyridine two carboxylic acid ligand. Synthesis of skeleton materials and their properties for gas adsorption: a novel T - shaped pyridine two carboxylic acid ligand 4? - (pyridine -4- based) -[1,1? Biphenyl]-3,5- two carboxylic acid (H_2PBPD) was synthesized by Suzuki coupling reaction. In solvothermal condition, a novel three-dimensional metal organic skeleton porous structure was formed by H_2PBPD ligands and copper ions in a solvothermal condition The material [Cu (PBPD) (DMF) _2 (H_2O) _3] (compound 4). The single crystal X- ray diffraction analysis shows that the compound crystallizes in the R-3 space group of the six square crystal system and is a three-dimensional structure of the 3,6 connection. The vertex symbol of the simplified topology is (4~2? 6) _2 (4~4??). The stability test shows that compound 4 is soaked for two months in different organic solvents and is in the process. In air atmosphere, 250 oC calcined for half an hour can maintain the original crystal structure.77 K nitrogen adsorption desorption test, which shows that the compound has microporous characteristics and its BET specific surface area is 1682 m~2g~ (-1). In addition, the absorption of the compound under 273 K atmospheric pressure on lower methane and carbon dioxide is 45 cm~3g~ (-1) and 114 cm~3 g~ (-1). Finally, The cyclic adsorption capacity of carbon dioxide was tested on compound 4. The test results showed that the adsorption capacity of compound 4 was not decreased after 10 cycles, and the original structure was maintained. The above experimental results showed that the ligand had a certain value in the preparation of MOFs materials with high stability and high adsorption properties.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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