可控形貌有机微孔聚合物空心微囊构建及其应用

Compared to the traditional microporous materials, microporous organic polymers (MOPs) have the advantages that they combine high surface areas with low skeleton density, good physical and chemical stability and synthetic diversity. However, due to the rigid aromatic building block, MOPs are mostly in powder form, which may narrow their application field. Morphology controllable MOPs may bring them more special features. Combined the hollow structure and microporous organic polymer, the HMOCs not only has high surface areas with good physical and chemical stability and synthetic diversity, but also has other special properties. This may strengthen the performance of materials and broaden the application field of MOPs. In this proposal, we aim to produce multifunctional hollow microporous organic capsules (HMOCs) with very high surface areas by using facile template polymerization with crosslinking or coupling reactions. The thickness of materials and the cavity size can be controlled by changing the amount of monomer and the size of inorganic particle templates. The specific surface area and pore structure of the material can be controlled by changing the amount of crosslinking agent. HMOCs with functional structure can be prepared by designed monomer. Furthermore, after embedding inorganic nanoparticles, HMOCs can contain the acoustic, magnetic, optical, thermal and other excellent properties of inorganic nanoparticles. The application of HMOCs on heterogeneous catalysis, drug delivery and gas separation will be explored. The results will help to construct a methodology to prepare morphology controllable MOPs with tremendous applications, that will benefit to the scientific research and industry as well.

与传统微孔材料相比，高比表面积的微孔有机聚合物（MOPs）具有密度低、稳定的理化性能、合成方法多样等优势而成为当前研究热点。MOPs的构建单元多采用芳环单体，因而其产物多为粉末状态，在一定程度限制了其应用范围。如构建形貌可控的MOPs，将赋予其更多特殊的功能。本项目拟采用模板法，通过交联、偶联等构筑形貌可控的多功能有机微孔聚合物空心微囊（HMOCs）。通过改变单体（种类、用量）、无机模板（形状、尺寸）、在空腔内包埋无机纳米颗粒、对囊壁进行改性修饰等手段，对HMOCs的形貌（壁厚、空腔尺寸）、囊壁化学结构、材料性能（比表面积、孔结构）进行调节，制备得到多功能的HMOCs，并初步探索其在多相催化、药物释放及气体分离等方面的应用。研究结果将有助于构建微孔有机聚合物的形貌控制方法体系，扩展MOPs的实际应用范围。

微孔有机聚合物（MOPs）因其高比表面积和结构基元多元化等优点得到研究者的关注，并在吸附与分离、催化等领域应用广泛。目前对MOPs的研究主要集中在材料制备及孔径调节的研究，对形貌控制研究较少。根据结构与性能的关系，若能够精准调控分子链的排布堆积方式，实现对MOPs微观形貌的控制，发展微观形貌可控的微孔有机聚合物材料并赋予材料功能化将会对MOPs领域的有重大影响。本项目基于对超交联微孔聚合物（HCPs）的研究基础上，采用模板法制备有机微孔聚合物空心微囊（HMOCs），赋予微囊材料多元化功能性，并探索其在气体吸附与分离领域、催化及光电和生物医药领域有着重要的价值。代表性的研究成果包括：以SiO2为模板制备了中空的HCP微球，该材料可作为载体实现药物吗啡的缓慢释放；制备有机微孔空心微囊（HMOCs）并将其碳化应用于超级电容器显示出了高比容量和循环稳定性；发展制备一类酸碱共固载的HMOCs，材料表面均匀分布的酸性和碱性官能团使其在多种串联反应中有着高效的催化效率；将磁性Fe3O4包埋在HCP内形成磁性的有机微囊结构材料，对罗丹明B的吸附容量高达215 mg/g。在本项目的资助下，项目负责人以通讯作者在Chem Soc Rev、Nat Commun、Sci Adv、Angew Chem Int Ed、Chem Commun、Macromolecules 等期刊发表SCI论文，并获得了38篇，学术专著1项。