基于多氮唑-羧酸双官能团配体的金属有机骨架材料的合成、结构与吸附分离性能

Metal-organic Frameworks are a new class of porous material and have already currently become a hot topic of material fields because of their potential applications as separation, catalysis, molecular storage,ion exchange and molecular magnets. Especially, they have attracted more attentions for their merits on facile gas/solvent preparations because the process of selective adsorptions for this kind of porous material can overcome the shortcomings of the conventional methods requiring special low temperature and high pressure, and/or large energy-consuming fractional process. This project will adopt the bifunctional organic ligands containing azolate and carboxylate groups, vary the subsitituent groups, the type of azolate, and the relative position and number with carboxylate groups in order to adjust the framework and pore structure, and seek for the controlling synthesis conditions by using different metal ions with diverse coordination modes and changing the diverse experiment conditions. Moreover, on the basis of the structures of the frameworks defined by single crystal and powder X-ray diffraction, the systemic information will be acquired and the relationship between the structures and properties are summarized by studying the properties of sorption and separation through sorption measurements, which provide new methods for the design and synthesis of novel functional metal-organic frameworks with large uptake capacity and selective separation properties, and develop new porous materials with highly separation properties in order to reduce large industrial energy-consuming process.

金属有机骨架作为一种新型多孔材料，由于在分离、催化、气体贮存、离子交换、分子磁体等方面具有广泛的应用前景正成为材料领域一大研究热点。此类材料的选择性吸附作用可克服传统方法上气体/溶剂分子分离所需的低温和高压的条件，或高耗能的分馏步骤。因此，该类材料在气体/溶剂分子的选择性分离领域的研究备受关注。本项目拟采用含多氮唑与羧酸双官能团的有机桥联配体，通过取代基的改变、多氮唑基团类型及其与羧酸相对位置和个数的改变，不同配位特性的金属离子和实验条件的选择，来调控金属有机骨架的结构及其孔结构，探索该类材料的控制合成条件。在单晶和粉末X-衍射确定其空间结构的基础上，通过吸附测试手段研究对气体和溶剂分子的吸附与选择性分离性能，获得比较系统的信息，总结其构效关系，为定向组装具有高效吸附和选择性分离功能的金属有机骨架化合物提供经验和规律，并开发出具有选择性高效分离功能的新型多孔材料，降低工业能耗的目的。

金属有机骨架作为一种新型多孔材料，由于在分离、催化、气体贮存、离子交换、分子磁体等方面具有广泛的应用前景正成为材料领域一大研究热点。本项目采用三氮唑和羧酸混合配体、以及多氮唑-羧酸双官能团的有机桥联配体，通过多氮唑基团类型及其与羧酸相对位置的改变，不同配位特性的金属离子和实验条件的选择，探索该类化合物的控制合成条件，组装得到21个结构新颖的氮唑羧酸配位化合物，为定向组装金属有机骨架化合物提供经验和规律。利用单晶衍射、粉末衍射、红外和元素分析表征化合物的组成，利用气体吸附测试表征了多孔性能及分离性能，利用热重分析和荧光测试表征化合物的热稳定性和发光性能。研究发现3-甲基取代的三氮唑配体、羧酸和金属锌离子组装三元体系金属有机骨架Zn(II)/triazolate/OAc-具有选择性吸附CO2的功能，可以用于气态小分子N2和CO2的分离；合成的三氮唑-羧酸金属有机骨架[Cd2(1-tba)3Cl]既可以用于N2和CO2的分离，也可以识别芳香分子中的硝基苯和N,N二甲基苯胺；由三氮唑羧酸配体构筑的一维链状银配合物可以传感稀土离子发光；由三氮唑羧酸配体构筑的异核3d-4f骨架具有高连接性，且由于阴离子交换能力，可用于阴离子交换；由四氮唑羧酸配体构筑的异核3d-4f骨架具有客体依赖的颜色变化和客体依赖的荧光性质，可以用于芳香分子的识别。