基于金属卟啉和酞菁结构的三维共价有机框架材料的设计合成及催化性能研究

共价有机框架材料(COFs)是一类新型的结晶性有机多孔聚合物，由构筑单元在原子尺度上精确排列而形成有序的骨架和孔道结构，具有质量轻、结构可调控、易功能化等优点，在诸多领域拥有广阔的应用前景。目前已报道的COFs材料绝大多数为二维层状结构，对三维COFs的种类和性能研究的报道相对较少，同时COFs材料在催化领域的应用仍有待进一步开发。本项目拟基于三维COFs材料的设计理念，将金属卟啉和酞菁作为构筑单元通过共价键的方式连接制备具有催化活性的新型三维COFs材料，并将其应用于多相催化方面的研究。金属卟啉和酞菁作为催化活性位点有序地分布在材料当中，刚性的骨架结构使得这些功能分子避免发生聚集而失活，开放的孔道结构的富集效应有利于底物与催化位点的高效接触，从而有助于提高材料的催化效果，同时还可以实现催化剂的回收和循环使用。本项目将为拓展功能化COFs材料的种类以及在催化领域的应用发展提供新的思路。

Covalent organic frameworks (COFs) are a new class of crystalline porous polymers that allow the atomically precise integration of desirable π units to create predesigned skeletons and nanopores in bulky solids and thin films, and their unique features of well-defined crystalline porous structure, high stability together with tailored functionalities make them promising materials for many applications. Up to data, the major researches on COFs are usually limited in two-dimensional COFs, while the preparation and functional exploration of three-dimensional COFs (3D COFs) are still rarely reported. Moreover, it is worthwhile to further develop their applications in catalysis field. In this project, metalloporphyrin or metallophthalocyanine based 3D COFs will be designed and synthesized by using metalloporphyrins or metallophthalocyanines as functional building blocks, and develop their applications in catalyzing the heterogeneous reactions. The rigid skeleton structure, in which metalloporphyrins or metallophthalocyanines as catalytic sites distribute in ordered and separated, could avoid the catalysts deactivation due to the aggregations. The enrichment effects of their opening porous structures may also be beneficial to contacting efficiency of substrates and catalytic sites, and then improve the catalytic activity. Furthermore, using stable and insoluble porous materials as heterogeneous catalysts is favorable to the recovery and recycling of catalysts. This project is expected to provide new approaches to the development of functionalized COFs in heterogeneous catalysis application.