多孔超分子骨架材料的设计合成及其吸附与分离性能研究

Porous supramolecular framework materials represent a class of chemistry materials with definitive molecular structures, ordered pore structures, high surface areas and crystallinity. They have been found great competity and potentials for practical use in the areas of optics, electronics, magnetism, catalysis, and especially in molecular storage and separation. The current synthetic method for supramolecular framework materials involves mainly solvated crystllization. In such a way, the porous materials are dependent to solvents, which results in strcutural collapse upon sample activation and the porosity can hardly be sustainable. This project aims to develop a binary assembly strategy, which depends mainly on the supramolecular interactions between two functionalized molecular units to maintain the framework stability, available for the design and synthesis of supramolecular framework materials with optimized structural stability and porosity. Meanwhile, the storage and separation property of supramolecular framework materials can be manipulated by the functional and decorating groups of molecular units, which will underpin the study of structure-function relationships of new porous materials and offer key information for the research and development of effective porous supramolecular framework materials related for applications in storage, separation and beyond.

多孔超分子骨架材料由于其特定的分子结构、高度的结晶性、有序的孔结构、高比表面积等优点，在光电磁、催化、医药，尤其在分子吸附、存储与分离等领域表现出极大的竞争力和潜在的应用价值。目前超分子骨架材料的合成主要是溶剂化结晶法，这种方法得到的多孔材料对溶剂分子的依赖性导致材料活化后孔结构坍塌，很难维持材料的永久多孔性。本项目拟采取双组份协同组装的合成策略，依靠不同分子基元的官能团之间形成的超分子作用力来维持多孔材料骨架的稳定性，以实现结构、孔道稳定性优越的超分子骨架材料的设计合成。同时，通过调节分子基元的官能团和修饰基团来调控超分子骨架材料的储存与分离性能，侧重“结构-性能”的构效关系研究，为新型、高效多孔超分子骨架材料的研发及其在储存与分离等相关领域的应用前景提供重要的基础信息。

本项目采用可控自组装法合成多孔超分子骨架材料（SOFs），并利用其高度的结晶性、有序的孔结构、高比表面积等优点，开发SOFs材料在分子吸附、存储与分离领域的潜在应用价值。在研究计划的执行过程中，制备了两个系列13种SOFs材料，并系统地研究了他们的结构和各类物理化学性能，得到了具有良好分子吸附、存储与分离的多孔超分子骨架材料。其中氢键构筑的多孔超分子骨架材料表现出较高的热稳定性和永久性孔隙，并在CO2吸附与分离领域表现出优异性能；氢键-卤键协同组装的多孔超分子骨架材料表现出客体依赖的单晶结构转化性能，并重点研究了这两个体系中“结构-性能”的构效关系，为多孔超分子骨架材料的研究拓展了一个新方向。发表了12篇SCI论文，申请了2项专利，1名硕士生毕业取得学位。另有2名博士生和6名硕士生参与项目研究。