含氮杂环卡宾金属-有机框架材料后合成修饰及其对二氧化碳催化转化研究

Metal-organic frameworks (MOFs) have great potential for application in many fields due to their high surface area, ordered pores, tunable structures, numerous topologies and properties. At present, it is a focus of intensive research to explore how to enhance and extend the function of MOFs. This project will center on the catalytic conversion of greenhouse gas CO2 to solve real-world environmental problems. Specifically, it aims to introduce functional metal ions groups or noble metal nanoparticles, respectively by using the strategies of “post synthetic modification” for the construction of N-heterocyclic carbene (NHC) MOFs, and after that the modified NHC-MOFs could be used as high catalysts to enhance the reaction efficiency of CO2 and increase the reaction types. The research will concentrate on several functional systems. The first one involves the design and synthesis of a series of new organic ligands with NHC groups and the subsequent construction of various NHC-MOFs structures. Then more importantly, via “post synthetic modification”, functional transition metal ions, noble metal ion groups and noble metal nanoparticles will be grafted into the novel NHC-MOFs, respectively. The modified NHC-MOFs will act as catalysts in the reaction of CO2. Meanwhile, theoretical calculation will be used to guide and optimize the reaction conditions and structural design. Finally, the results of this project can provide effective strategies and sound theoretical basis for the synthesis of new catalytic MOF materials with superior performance.

金属-有机框架(MOFs)材料具有比表面积高、孔道规则、结构易修饰和拓扑结构丰富等特点，在众多领域有广泛的应用前景，如何拓展并提升其功能是目前研究的重要科学问题。本项目从催化转化CO2，解决现实环境问题出发，拟通过后合成修饰法在含氮杂环卡宾基团(NHC)的MOFs中引入功能性基团，旨在实现提高MOFs材料对CO2催化转化能力的目标。研究内容包括：设计合成含NHC的新颖配体，并构筑不同结构的NHC-MOFs；重点通过后合成修饰法，在NHC-MOFs中分别引入过渡金属离子(基团)，贵金属离子(基团)或贵金属纳米粒子等目标功能基团；对后合成修饰的功能NHC-MOFs进行CO2催化转化研究。项目将通过理论计算模拟指导、优化反应条件和结构设计，研究NHC功能基团与后合成修饰功能基团协同催化CO2的反应机制，探索结构-功能的关系，从而为进一步设计和获得性能优异的MOFs催化材料提供新的合成策略和理论。

金属有机骨架材料（MOFs）和有机共价多孔聚合物材料（COFs）具有较高的比表面积、结构的可修饰剪裁等特点，在催化、气体吸附分离、荧光探针等方面具有广泛的应用。本项目研究通过高密度不饱和金属中心、高路易斯碱功能位点、氨基功能化后修饰等方案，开展了金属-有机骨架化合物材料和有机共价多孔聚合物材料的合成与性质研究工作，合成了具有富含Re功能单元、路易斯碱位点、不饱和活性金属中心等系列具有不同功能化位点的MOFs和COFs材料，研究了这些材料在CO2光催化转化、异相协同催化、气体选择性吸附分离、分子荧光探针检测、锂离子电池负极材料等方面的应用，并系统总结了多孔材料在光催化CO2还原中面临的挑战和机遇，探索了合成条件对材料自组装的影响，为设计新型多孔材料提供了实验基础和理论依据。