多羧酸类金属—有机杂化材料的功能化设计及其性质研究

发布时间：2018-01-04 09:50

  本文关键词：多羧酸类金属—有机杂化材料的功能化设计及其性质研究　出处：《苏州大学》2015年硕士论文　论文类型：学位论文

  更多相关文章： 多羧酸类配体 气体选择性吸附 晶体结构转变 能量可控释放

【摘要】：晶体工程学为实现分子堆积的可设计性和可控合成,并进而实现材料的功能化提供了丰富的途径。金属-有机框架作为晶体工程学中的一类重要研究对象,以其结构稳定、设计多样、易于合成的优点,受到人们的广泛关注。而羧酸根容易与金属离子螯合形成稳定结构,所以多羧酸类配体通常被认为是构建金属-有机框架的优秀结构单元。本文主要利用水热与溶剂热合成的方法,通过控制反应温度、改变配体、调整反应物比例、调节酸碱度等策略合成了6个多羧酸基的金属-有机框架材料。采用X-射线单晶衍射确定了所获晶体的原子结构,并通过粉末X-射线衍射、红外光谱、热重分析、气体吸附、量热分析等表征方法对产物的结构以及性质进行了分析。主要内容如下:1.双羧基微孔框架的设计、合成,及其气体选择性吸附性质的研究。溶剂热条件下,将间苯二甲酸(1,3-H2bdc)和对苯二甲酸(1,4-H2bdc)分别引入硝酸铟(In(NO3)3)体系中,获得了两种具有不同孔状结构的金属-有机杂化材料,化合物1和化合物2:[H2In3O(OH)3(1,3-bdc)3](1)[HIn(1,4-bdc)2](2)化合物1中的孔道被其内部的苯环所阻挡,没有表现出对气体的良好的吸附能力。化合物2则在1 atm下对CO2和N2具有较高的吸附选择性,而且拥有良好的结构与气体吸附量的稳定性。2.能量的储存与pH控制释放。水热条件下,将1,3-二吡啶基丙烷(bpp)引入到醋酸钴(Co(Ac)2)和均苯四羧酸(1,2,4,5-H4btec)体系当中,制备了化合物3。将化合物3的样品放入酸性水溶液,保持常温常压(NTP:~298 K,1 atm),依次获得了化合物4,5和6:[Co5(OH)2(bpp)(btec)2]2?H2O(3)[Co2(H2O)4(bpp)2(Hbtec)2]?5H2O?H2bpp(4)[Co2(H2O)2(OH)(bpp)2(Hbpp)(btec)]?5H2O(5)[Co3(H2O)4(Hbpp)2(btec)2]?6H2O(6)值得一提的是,如果将原料混合,不经水热处理,空气中保持常温常压(NTP:~298 K,1 atm),会直接获得化合物6。将化合物6加水进行水热处理又会获得化合物3。在化合物转变的过程当中,体系的能量变化可以通过体系温度的波动以及理论计算得到验证。进一步实验表明,这种转变过程是可以通过调节体系的pH值来控制的。
[Abstract]:For crystal engineering design and implementation of controllable synthesis of molecular packing, and then realize the function of material provides a rich way. Metal organic framework as an important research object in crystal engineering, with its stable structure, design diversity, the advantages of easy synthesis, people pay more and more attention. And the CMC easy acid chelating with metal ions to form a stable structure, so the multicarboxylic acids are usually considered excellent building blocks of metal organic frameworks. This paper mainly uses the method of hydrothermal and solvothermal synthesis, by controlling the reaction temperature, reactant ratio change of ligand, adjustment, more than 6 carboxylic acid metal organic frameworks the material synthesized pH adjustment strategies are determined. The atomic structure of the crystal by X- ray diffraction and by powder X- ray diffraction, infrared spectroscopy, thermogravimetric analysis, gas adsorption, Calorimetry characterization methods of the product structure and properties are analyzed. The main contents are as follows: design, synthesis of 1. double carboxyl microporous framework, and Study on gas selective adsorption properties. Under solvothermal conditions, the benzene between two formic acid (1,3-H2bdc) and terephthalic acid (1,4-H2bdc) were introduced into indium nitrate (In (NO3 3)) system, obtained with two different porous metal organic hybrid materials, compounds 1 and 2:[H2In3O (OH) 3 (1,3-bdc) 3] (1) [HIn (1,4-bdc) 2] (2) channels in compound 1 is blocked by the Department of the benzene ring, did not show the the gas has good adsorption capability. The adsorption selectivity of compound 2 under 1 atm of CO2 and N2 is high, the release of stored energy control and the stability of pH.2. and has a good structure and gas adsorption capacity. Under hydrothermal conditions, 1,3- two pyridyl propane (BPP) into vinegar 閰搁挻(Co(Ac)2)鍜屽潎鑻�鍥涚晶閰�(1,2,4,5-H4btec)浣撶郴褰撲腑,鍒跺�囦簡鍖栧悎鐗�3.灏嗗寲鍚堢墿3鐨勬牱鍝佹斁鍏ラ吀鎬ф按婧舵恫,淇濇寔甯告俯甯稿帇(NTP:~298 K,1 atm),渚濇�¤幏寰椾簡鍖栧悎鐗�4,5鍜，

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