基于芳香四酸的金属有机骨架材料：合成、结构表征与气体吸附性能的研究

发布时间：2018-04-30 06:35

本文选题：金属-有机骨架材料 + 配体的功能化　；参考：《浙江师范大学》2016年硕士论文

【摘要】：金属-有机骨架材料(MOFs),也就是多孔配位聚合物(PCPs),是由金属离子或金属簇(SBUs)与多齿有机桥联配体通过金属配位键自组装形成的一类多孔结晶材料。由于具有比表面积大、孔径大小可调节、孔表面可功能化等突出特点,在气体储存、气体分离、多相催化,分子识别、药物运输等领域得到了广泛的应用。在众多的MOFs中,由方形的二铜次级结构单元和四连接的二(间苯二甲酸)有机配体形成的NbO型网络结构的MOFs得到了人们的广泛关注。因为它们具有开放的金属位点和用于气体储存的两种不同类型的纳米笼,适宜于气体储存。更重要的是,当不同的官能团嫁接在二(间苯二甲酸)有机配体中,在大多数情况下,相应的骨架仍采用相同的NbO类型结构,这样就为研究功能性基团在气体吸附中的影响提供了理想的平台。因此,本论文的主要研究内容如下：1、用于存储甲烷的MOFs设计合成为了通过孔径的优化来提高甲烷吸附,设计合成了两个含有C≡C的四羧酸配体5,5’-(苯-1,4-取代-乙炔-1,2-取代)二(间苯二甲酸)和5,5’-(萘-1,4-取代-乙炔-1,2-取代)二(间苯二甲酸),溶剂热条件下与Cu~(2+)反应制备了两个同型结构的MOFs:ZJNU-50和ZJNU-53 。材料经活化以后,在298 K、65 bar条件下它们单位体积内甲烷吸附量分别是229 cm~3 (STP) cm~(-3)和241 cm~3 (STP) cm~(-3);在5-65bar工作区间内,单位体积内甲烷工作量分别为184 cm~3 (STP) cm~(-3)和190 cm~3 (STP) cm~(-3) 。在已报道的MOFs中,这些值都是特别高的。2、用于捕获二氧化碳的MOFs设计合成设计合成了含有不同极性杂环基团(VA二唑、噻二唑、硒二唑)的三个二(间苯二甲酸)有机配体,采用溶剂热法与Cu~(2+)反应合成了三个MOFs:ZJNU-41、 ZJNU-40和ZJNU-42。三个材料经活化后,在298 K、1 bar条件下CO_2的吸附量分别为97.4、85.7和37.6cm~3(STP)g-1;实验结果显示随着引进杂环极性的增大,CO_2的吸附量依次增加,实验结果与分子模拟计算是一致的,说明在骨架中引入高极性杂环能够提高MOFs对CO_2的吸附能力。设计合成了三个氮原子数目和方向不同的二(间苯二甲酸)有机配体：5,5’-(喹啉-5,8-取代)-二(间苯二甲酸)、5,5’-(异喹啉-5,8-取代基)-二(间苯二甲酸)和5,5’-(苯并吡嗪-5,8-取代基)-二(间苯二甲酸)。溶剂热条件下与Cu~(2+)反应制备了三个同型拓扑结构MOFs:ZJNU-43. ZJNU-44和ZJNU-45。三个材料经活化以后,在296 K、1 bar条件下,CO_2吸附量分别为103、116和107 cm~3 (STP)g-1。尽管它们具有相似的孔隙率,ZJNU-44a的CO_2吸附量比ZJNU-43a和ZJNU-45a都高,实验结果说明MOFs对CO_2的吸附性能不仅与碱性氮原子数目有关而且还和方向有关。3、用于存储乙炔的MOFs设计合成设计合成了三个含氮原子杂环的二(间苯二甲酸)有机配体：5,5’-(吡嗪-2,5-取代)二(间苯二甲酸)、5,5’-(哒嗪-3,6-取代)二(间苯二甲酸)、5,5’-(嘧啶-2,5-取代)二(间苯二甲酸),溶剂热条件下与Cu~(2+)反应,得到三个同型结构MOFs:ZJNU-46、 ZJNU-47和ZJNU-48。三个材料经活化后,在295 K、1 bar条件下,乙炔吸附量分别为187、213和193 cm 3(STP) g-1.虽然它们几乎具有相同的孔隙率、开放的金属位点和未配位的碱性氮原子位点,在这三个材料中ZJNU-47a乙炔的吸附量最高,在所有报道的MOFs中处于第二。说明了合理的设计骨架中开放的碱性氮原子位点能够增强对C2H2的吸附。
[Abstract]:Metal organic framework material (MOFs), which is a porous coordination polymer (PCPs), is a kind of porous crystalline material formed by metal ions or metal clusters (SBUs) and multi tooth organic bridging ligands through metal coordination bonds. Gas separation, polyphase catalysis, molecular recognition, drug transport and other fields have been widely used. In many MOFs, the MOFs of the NbO type network structure formed by the square two copper secondary structure unit and the four connected two (interphenyl two formic acid) organic ligand has been widely concerned because they have open metal loci and use. Two different types of nanoscale in gas storage are suitable for gas storage. More importantly, when different functional groups are grafted in two (interphenylene two formic acid) organic ligands, in most cases the corresponding framework still uses the same NbO type structure, which provides ideal for the study of the effect of functional groups on gas absorption. The main contents of this paper are as follows: 1, the design and synthesis of MOFs for storing methane is designed to improve the adsorption of methane through the optimization of the aperture, and the design and synthesis of two four carboxylic acid ligands containing C C - (benzene -1,4- substituted acetylene -1,2- substitution) two (interphenyl two formic acid) and 5,5 '- (naphthalene -1,4- substituted acetylene -1,2- substitution) Two (interphenyl two formic acid), two identical structures of MOFs:ZJNU-50 and ZJNU-53 were prepared under the solvothermal condition with Cu~ (2+). After activation, the amount of methane adsorption within the unit volume was 229 cm~3 (STP) cm~ (-3) and 241 cm~3 (STP) under the condition of 298 K and 65 bar; within the working interval, methane workers in the unit volume. The quantities are 184 cm~3 (STP) cm~ (-3) and 190 cm~3 (STP) cm~ (-3) respectively. In the reported MOFs, these values are particularly high.2. The MOFs design synthesis design for capturing carbon dioxide is designed to synthesize three two (interphenyl two formic acid) organic ligands containing different polar heterocyclic groups (VA two azole, thiothiazole, selenium two azole). The u~ (2+) reaction synthesized three MOFs:ZJNU-41, ZJNU-40 and ZJNU-42. three materials after activation. The adsorption amount of CO_2 was 97.4,85.7 and 37.6cm~3 (STP) under the conditions of 298 K and 1 bar, respectively. The experimental results showed that the adsorption amount increased in turn with the increase of the polarity of the imported heterocyclic ring, and the experimental results were in agreement with the molecular simulation calculation. The introduction of high polar heterocycles in the skeleton can improve the adsorption capacity of MOFs to CO_2. Three organic ligands with different nitrogen atoms and different directions are designed and synthesized: 5,5 '- (quinoline -5,8- substitution) - two (interphenyl two formic acid), 5,5' - (isoquinoline -5,8- substituent) - two (interphenylene two formic acid) and 5,5 '- (benzopirzine -5,8- substituent) - Two (interphenylene two formic acid). Under the solvothermal condition, three identical topologies of MOFs:ZJNU-43. ZJNU-44 and ZJNU-45. were prepared by the reaction with Cu~ (2+). After activation, the adsorption capacity of CO_2 was 103116 and 107 cm~3 (STP) g-1., under the 296 K and 1 bar conditions, although they had similar porosity. NU-45a is high. The experimental results show that the adsorption properties of MOFs on CO_2 are not only related to the number of basic nitrogen atoms but also related to the direction of.3. The design and synthesis of MOFs for acetylene synthesis design and synthesis of three nitrogen containing heterocyclic heterocyclic two (interphenyl two formic acid) organic ligands: 5,5 '- (pyrazine -2,5- substitution) two (interphenyl two formic acid), 5,5' - (pyridazine -3,6) - substituted) two (diphenyl two formic acid), 5,5 '- (pyrimidine -2,5- substituted) two (diphenyl two formic acid), reaction with Cu~ (2+) under solvent thermal conditions, and obtained three homostructure MOFs:ZJNU-46, ZJNU-47 and ZJNU-48. three materials after activation, 295 K, 1 bar, respectively, the acetylene adsorption amount is 187213 and 193 cm 3 (STP) g-1. although they almost have the same The porosity, the open metal site and the uncoordinated basic nitrogen atom site, the highest adsorption capacity of ZJNU-47a acetylene in these three materials is second in all reported MOFs. It shows that the rational design skeleton of the open basic nitrogen atom site can enhance the adsorption of C2H2.

【学位授予单位】：浙江师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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