氟簇基金属有机框架材料设计合成与疏水亲油性能研究

As a unique class of porous crystalline materials, metal-organic frameworks (MOFs) are obtained from the self-assembly of metal ions or metallic clusters and organic linkers. Owing to extra large specific surface areas and porosity, and tunable nanopore environments, MOFs are of great potentials to many applications, such as gas storage, selective sorption and separation, chemical sensing, drug delivery and release, host-guest recognition etc. However, very few studies have been dedicated to MOFs as oil-water materials because of most of MOFs unstability of water or moisture, and only a few examples of the hydrophobic MOFs. According to our previous studies, we proposed a novel method to prepare metal fluoride organic frameworks (MFOFs) base on metal fluoride clusters. MFOFs belong to hydrophobic/oleophilic materials and have potential applied in water-oil separation. The project focuses on design and synthesis of a new kind of hydrophobic MOFs by incorporating hydrophobic fluorinatied functional groups in metal clusters as nodes through in-situ or post-synthetic modification. Simultaneity, the interaction mechanism between the metal fluoride clusters, pore types, pore sizes and vapor adsorption property will be deeply studied. This project will explore the relationship among the self-assembly, structures and properties of such materials, to provide experimental guidance and theoretical basis for the controlled synthesis of water-stable and hydrophobic MOFs with potential application in oil-water separation, and promote research and development of this field.

目前，对于金属有机框架（MOFs）材料的研究主要集中在气体储存与分离等领域的应用，将其应用于油水分离方面是当前研究的前沿课题。申请人在前期工作的基础上，提出了一种以金属氟簇为节点制备氟簇基MOFs材料的新思路。研究发现，新型氟簇基MOFs材料具有疏水亲油的特点，在油水分离方面有着潜在的应用价值，而其金属氟簇节点的形成机理及微观结构调控机制有待深入研究。本项目拟采用原位生成或后合成修饰法将疏水性氟元素引入到金属簇节点中，设计合成不同金属氟簇节点类型的氟簇基MOFs材料，详细研究金属氟簇结构单元类型、孔洞性质和孔径大小对水蒸汽和石油成分中烃类有机蒸汽的作用规律，探究氟簇基MOFs材料的油水作用机制及吸附分离机理，总结合成-结构-性能三者之间的关系，发展一套制备新型疏水性MOFs材料的设计方法和定向合成路线，最终为可控合成具有应用前景的油水分离材料提供理论依据和实验基础。

为了对油中烷烃类物质获得高效的分离效果，需要更进一步开发出同时具有高比表面积和高选择性的新型多孔吸附材料。本项目通过引入金属氟簇节点，设计合成了系列稳定性好且高吸附选择性的新型氟簇基MOFs材料，系统地研究该类材料结构、性能及吸附分离机制间的关系，确立了金属氟簇节点构筑MOFs材料的新策略，并开发出超四面体结构单元构筑的新型介孔MOFs中，为发展用于油中烷烃类物质分离的新型多孔材料提供理论和实验依据。在本项目研究过程中，发表有该基金资助号的学术论文10篇，申请国内发明专利1项，培养了3硕士研究生。