多咪唑修饰超分子金属有机框架（MOFs)构建和性能研究

1. Crystal Design and Growth of the Metal Organic Frameworks with Novel Structure, Outstanding Performance on Fluorescence, Magnetic and Catalyze..In order to obtain ideal targeting MOFs for smart sensors and recycle organic pollutants, Separation,adsorbed gas and catalytic electrolysis of water. This project will focus our efforts on the design and synthesis these excellent material with the aromatic acid based on the theoretical support of crystallography, coordination chemistry and the following three class of organic compound: ① the polyimidazole calixarene compound which with special and adjustable cavity. ② the N-functionalized calixarene fragment and ③ the Imidazole modified porphyrin derivatives with biochemical activity. Meanwhile, we can summarize some rules during the preparation of the result MOFs.2. Characterization and Research the Performance and Application on Pollutants Sensing, Electrolysis of Water, Adsorption for Gas of the Achieved MOFs..The result MOFs can be characterized by recent technology and method, such as single crystal X-ray diffraction, elemental analysis, power X-ray diffraction (PXRD), IR spectroscopy, and thermogravimetry, and so on. To study the characters of these MOFs, and on the basis of which to explore mechanism of photoluminescence between nitro pollutants and synthetic MOFs, and which of catalytic for electrolysis of water, which of gas adsorption, as well, then further used in pollutants sensing, detection and governance, electrolysis of water , adsorption for gas..3. The Goals of the Project..The aims of this project contain: I) obtaining a series of MOFs which exhibit outstanding performance on fluorescence, magnetism,and porosity and the relative mechanism; II) Sensing the nitro organic pollutants, and further used for air, water and soil pollution; III) Setting up the system of catalytic electrolysis of water to get the hydrogen and oxygen.

围绕设计并合成结构新颖、具有荧光、磁性、多空隙等良好性能的MOFs材料，使此类材料具有可对硝基类有机污染物灵敏传感和富集，能有效催化电解水，具有较强的吸附分离气体的能力。为此，本项目拟基于①结构特殊、可调空腔的杯芳烃，②功能化修饰的杯芳烃碎片, ③具有生化活性的卟啉或金属卟啉这等三类的多咪唑化合物，通过引入骨架可变的辅助羧酸类配体和金属离子以晶体学、配位化学为理论支撑，构筑成一系列相应的MOFs。同时，总结出这类MOFs组装过程的一些规律。以X单晶衍射、元素分析、粉末单晶衍射、热重分析、红外波谱分析等现代技术对其进行结构表征和性能的研究。并鉴于此，探究这类MOFs与硝基类有机污染物和其他小分子的荧光作用、催化和吸附机理，进一步将其应用于大气、水污染处理，并以此类材料为催化剂建立电解水析氢、析氧体系。

（MOFs）是由无机金属中心（节点）和桥连的有机配体（连接器）通过自组装构成的具有周期性网状多孔状晶态材料，其结构具有有序性，可裁剪性和微孔性，同时具有机、无机材料的性能，为构筑结构新颖，功能多样性的MOFs提供了结构基础。本项目以多咪唑有机配体的构建MOFs及性能研究，以金属离子与多咪唑配体合成的沸石类材料（MOFs）为研究的主要对象，其主要内容为：1）双咪唑有机配体：2-（1H-咪唑-甲基）-6-（3--（1H-咪唑-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚、1，5-二咪唑蒽、1，4=二咪唑丁烷，新的双咪唑有机配体、多元芳酸和金属离子（Co2+，Zn2+,Cd2+等）通过多种合成方法相应晶体材料，对硝酸镁、硝基苯有良好选择性识别。2）多咪唑有机配体：四咪唑四苯乙烯、四咪唑卟啉、四咪唑四苯基吡嗪、三咪唑三苯胺，多元芳酸和金属离子（ Cu2+，Ni2+，Co2+，Zn2+,Cd2+等）通过多种合成方法相应金属有机框架材料，在水溶液对三价铁离子和TNP具有优良的作用，同时有多识别有毒物质的作用，研究表明对催化叠氮与炔的Click反应具有高的催化活性和广适性。3）多元芳香酸：2-硝基3，4，，5-联苯三羧酸，2,​3,​5,​6-四(4-羧基苯基l)​吡嗪与金属离子（镧系金属离子，Mn2+，Cu2+，Co2+，Zn2+,Cd2+等）形成的MOFs，在水相组氨酸，冬氨酸、硝基化合物等有优良的作用，双金属MOFs对电解水析氢、吸氧进行详细研究。