8-羟基喹啉类金属-有机框架的设计合成及异相催化性能研究

In recent years, using metal-organic frameworks (MOFs) as heterogeneous catalysts has received considerable attention because the catalytic functionalities are designable and controllable versus traditional inorganic zeolites. Herein, a variety of multidentate organic ligands based on 8-hydroxyquinoline skeletons with different sizes, charges, geometries and functions will be designed and synthesized. Some ligands contain many functional groups such as -NH2, and -N3 et. al.. which will be contribute to the post-modification of MOFs. Based on coordination and supramolecular chemistry, various novel microporous metal-organic quilonine frameworks with catalytic activity will be prepared. Then the physical and chemical properties (such as pore and of chirality et. al.) of as-synthesized MOFs will be explored. Likewise, a special emphasis will be given to study the catalytic properties of MOFs in heterogeneous processes. Different size substrates are chosed to explore the activity, selectivity, and recyclability. Both modifying an organic ligand and postsynthetic modification with a wide range of groups are two important approaches for precisely tuning the surfaces and pores of MOFs. In this way, two types of complementary, systematic studies can be performed for the development of structure-function relationships based on the MOFs topology versus MOF functionality. However, above studies contribute us to design and synthesize some new MOF catalysts with improved catalytic activity and selectivity. Finally, we will conclude the relationships of methods of preparation, organic and inorganic components, crystal structure and catalytic properties for further synthesis of novel crystalline MOF catalysts.

相对无机沸石类催化剂，金属-有机框架材料具有更好的可设计和调控性的优点，因此其异相催化性能的研究近年来引起人们越来越多的关注。本项目拟以8-羟基喹啉骨架为平台，设计合成多种长度、电子、立体结构和功能不同的桥联多齿配体，其中部分配体含-NH2和-N3等可后修饰功能基团，基于配位化学和超分子原理，构筑各种具有微孔结构并兼具催化活性的金属-有机喹啉框架，研究它们的孔性质及其相关的手性等物理化学性质；深入研究合成材料的异相催化性能，选定不同尺寸底物考察催化剂的活性、选择性和循环使用性，并通过修饰或后修饰实现对材料的孔道和表面特性更精细的调控，揭示出此类催化剂微环境对催化性能的主要影响，进而获得催化功能增强型金属-有机框架催化剂。研究总结此类催化剂的制备方法、各组分结构、晶体结构和催化性能之间的关系，为进一步指导合成新型具有良好应用前景的晶态金属-有机框架催化剂奠定基础。

金属-有机框架材料，尤其是具有丰富的晶内孔道、表面结构和催化活性位点的框架材料，是近年来深受重视的一类多功能分子基材料。本项目以8-羟基喹啉骨架为平台，合成了多种长度、电子、立体结构和功能不同的桥联配体（如单吡啶和双吡啶基等），基于配位化学和超分子化学原理，制备和组装出多种孔洞尺寸和形貌不一的分子型或多维的金属-有机框架材料。通过合理选择有机配体和金属盐、阴离子调控以及辅助配体的引入等方法，探索和总结了8-羟基喹啉基金属-有机聚合物的形成规律和影响因素。根据合成材料的结构特征，选择合适的催化反应（如水氧化和Knoevenagel缩合反应等）研究金属-有机孔洞框架的催化效率和选择性；研究表明材料的孔道结构和金属活性位点间的协同效应有助于提高催化效率和选择性；此外，我们还合成了系列8-羟基喹啉类金属-有机簇合物并研究了其发光性能。在研究8-羟基喹啉基金属-有机材料结构与性能之间关系的基础上，总结了材料形成过程各基本结构单元的电子和空间结构、材料的制备和组装方法与目标结构和性能之间的关系，为发展新型的金属-有机框架化合物提供了科学依据。. 作为项目研究成果，共发表标注本项目资助论文17篇，其中7篇论文发表在IF大于4.0的国际权威期刊上。