基于共价作用的多孔框架化合物研究

朱广山+卜显和+孙福兴+常泽+景晓飞

摘 要：目前，性能优异的有机多孔材料已经成为多孔材料研究领域的热点及前沿问题。多孔共价有机框架材料作为一种新型的多孔材料，在结构和性质调控方面比传统的分子筛和MOFs材料更加灵活。现阶段，国内外关于有机多孔材料方面的研究集中在实验合成方法、材料在气体储存及作为催化剂载体等方面。虽然有机多孔材料具有高稳定性（热稳定性及化学稳定性）、较大的比表面积，但是在气体吸附（特别是在氢气储存方面）并没有表现出优异的性能。该课题组报道的PAF-1在77 K，48 bar下氢气储存质量百分数7 wt%，是有机多孔材料在氢气储存上最高的，同样也处于一系列多孔材料在氢气储存方面的前列。目前有机多孔材料的构筑基元多为具有刚性结构的多节点单体。由于材料的结构特点影响其性能，在已知报道的基础上，可以利用有机单体的多样性特点，在特定的聚合反应中引入可官能化的单体，这样就可以丰富有机多孔材料的结构，引入的官能团也可以有效地改变材料的性能，同时也利于材料在后修饰方面的开发应用。目前，虽然有机多孔材料在局部结构上具有一定的有序性，但是它们长程无序导致这类材料大多是无定形的，制备可以分析结构的结晶有机多孔材料也是研究的热点及前沿性问题。该课题将在已有积累的基础上，探索共价有机多孔材料的设计合成、结构调控以及与储气、分离、纯化等功能性之间的关联规律，寻找提高储气、分离材料各项性能指标的关键因素，以期获得新型高性能的多孔有机固体储气材料、分离材料。具体研究内容包括：（1）计算机理论模拟作为开展有机框架多孔材料研究的指导；（2）有机结构基元的设计与合成；（3）选择合适的制备有机框架多孔材料的聚合反应类型；（4）有机框架多孔材料的功能化探索。期望通过5年的研究，可以通过对材料的官能化，改变材料的性能，使材料在与能源及环境息息相关的领域，包括氢气、二氧化碳、甲烷储存及有机分子污染物吸附方面产生很好的应用前景。

关键词：有机多孔材料 气体吸附 孔框架化合物

Abstract：Currently， porous organic frameworks （POFs） has become a hot research field of porous materials. As a new type of porous material， their structure and nature of regulation are more modifiable than zeolites and metal-organic frameworks. At present， researches is concentrated in the experimental synthesis methods， their gas storage and catalysis properties. Although porous organic material have a high stability （thermal and chemical stability） and large specific surface area， they did not exhibit superior performance in the gas adsorption. Our research group reported PAF-1 at 77 K， 48 bar with a hydrogen storage of 7 wt%， the highest hydrogen storage among the porous organic materials， also at the forefront of the whole porous materials. Current organic monomers to construct the porous organic materials are mostly rigid. On the basis of the known report， we can use the characteristics of the diversity of organic monomers， in particular those may be introduced functional groups in the polymerization. And the introduction of functional groups can effectively change their gas adsorption properties. On the other hand， currently， although some of the porous organic materials have a partial order on the structure， they lead to long-range disorder. Crystalline porous organic materials whose structures can be analyzed are also the hot research frontier issues. This project will be on the basis of the existing accumulated results， and explore the design and synthesis of porous organic frameworks， study the association between the structural features and the properties of gas storage， separation and purification， look to the key factors to improve the gas storage and separation properties of various materials， and obtain porous organic materials with high performance of gas storage and separations. Specific studies will include： （1）computer simulation as the guiding to carry out organic porous materials research； （2）design and synthesis of organic monomers as building blocks； （4）select the type of polymerization reaction which are suitable for preparing the targeted organic porous materials； （4）explore the functions of these porous materials. It is expected， through five-year research， we can obtain a series of porous organic frameworks which have good potential applications in the energy and environmental fields， including the storage of hydrogen， carbon dioxide， and methane and the adsorption of pollutants products through the structure modification.

Key Words：Porous organic frameworks； Gas storage； Structure modification

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