混合配体金属有机骨架的合成及性能研究

发布时间：2018-01-10 01:18

本文关键词：混合配体金属有机骨架的合成及性能研究　出处：《北京工业大学》2016年硕士论文　论文类型：学位论文

【摘要】：金属有机骨架材料(MOFs)作为一类新型有机-无机杂化的多孔材料,以其在分离、催化、药物缓释、离子交换及荧光响应等方面的潜在应用而备受人们的关注。金属有机骨架材料在其多孔性、孔尺寸及形状的可调性、孔表面的可修饰性等方面都优于传统的多孔材料。此外,构筑金属有机骨架时,通过选择适当的配体,在一定程度上,可以为特定应用而定向调控MOFs材料的结构及性质。使用混合配体构筑MOFs的策略因其配位环境的改变,更容易合成出结构新颖、性质稳定并具有良好应用前景的MOFs材料。本论文选择4,8-二磺酸基-2,6-萘二羧酸(4,8-disulfonaphthalene-2,6-dicarboxylic acid,H4L)配体,并将含氮的吡啶衍生物作为辅助配体,分别与不同的金属盐(Zn(NO3)2和Cd(NO3)2)经一锅反应构筑了两种金属有机骨架材料(Me2NH2)2[Zn2L1.5bpy]·2DMF(BUT-201)及(Cd L0.5dpe0.5)·2H2O(BUT-202)。BUT-201是一种三维(three-dimensional,3D)柱状双层结构,骨架带有负电荷,孔内含有(CH3)2NH2+作为电荷平衡离子。实验发现,通过与(CH3)2NH2+进行阳离子客体分子交换作用,BUT-201可以选择性地吸附尺寸相对较小的阳离子型染料,对于尺寸较大的阳离子型染料及尺寸相当的中性和阴离子型染料则没有吸附现象。BUT-201对有机染料的吸附行为是由电荷及尺寸/形状效应共同控制的。此外,在饱和LiNO3的甲醇溶液中,吸附的染料可以逐渐释放。由于发光配体与金属中心的相互作用,BUT-202展现出优异的光致发光性质。在N,N-二甲基甲酰胺(N,N-Dimethylformamide,DMF)中,即使有其他硝基化合物存在竞争时,BUT-202也能快速并有选择性地响应硝基爆炸物2,4,6-三硝基苯酚(2,4,6-trinitrophenol,TNP)。实验表明,其良好的选择性是由电子及能量转移机制和TNP与骨架之间的氢键作用共同控制的。
[Abstract]:Metal organic frameworks (MOFs) as a new type of porous organic-inorganic hybrid, its separation, catalysis, drug delivery, potential applications of ion exchange and fluorescence response and has attracted much attention. The metal organic framework material in the porous, Kong Chi inch and adjustable in shape, porous materials the surface modification of the hole are better than traditional building. In addition, the metal organic framework, by choosing appropriate ligands, to a certain extent, for the structure and properties of a specific application of directional control MOFs materials. Using mixed ligands MOFs strategy because of its coordination environment change, more easily the synthesis of novel structure, stable and has good prospects for the application of MOFs materials. This paper selects 4,8- two -2,6- naphthalene sulfonic acid (4,8-disulfonaphthalene-2,6-dicarboxylic two acid, H4L) and the ligand, nitrogen containing pyrazole Pyridine derivatives as auxiliary ligands, respectively with different metal salts (Zn (NO3) 2 and Cd (NO3) 2) by one pot reaction to build two kinds of metal organic frameworks (Me2NH2) - 2DMF (BUT-201) and 2[Zn2L1.5bpy] (Cd L0.5dpe0.5) - 2H2O (BUT-202).BUT-201 is a three-dimensional (three-dimensional, 3D) columnar double-layer structure, skeleton with a negative charge, the hole containing (CH3) 2NH2+ as charge balance ion. The experimental results showed that, with the (CH3) 2NH2+ cation exchange of guest molecules, BUT-201 can selectively adsorb relatively small size of cationic dyes for neutral and anionic dye dye and considerable size there is no large cationic adsorption behavior of.BUT-201 adsorption phenomena of organic dyes by the charge and size / shape effect of common control. In addition, in methanol solution in LiNO3 saturated adsorption of the dye can be gradually released. The interaction of Yu Faguang ligands and metal centers, BUT-202 exhibits excellent light emitting properties. In two N, N- dimethylformamide (N, N-Dimethylformamide, DMF), even if there is competition of other nitro compounds, BUT-202 can quickly and selectively respond to nitrate based explosive 2,4,6- three nitro phenol (2,4,6-trinitrophenol, TNP). Experimental results show that the good selectivity is controlled by hydrogen bonding between electron transfer and energy transfer mechanism and TNP and the framework.

【学位授予单位】：北京工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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