含酞菁或卟啉配体的多孔配位骨架材料的设计及其作为碳捕获材料的研究

Porous Coordination Frameworks (PCF) are promising materials for carbon dioxide capture since they have abundant topology structures which can be easily modulated, high surface areas and low densities. Based on our theoretical research [J. Chem. Phys.，136, 234703 (2012)], we will apply first-principles calculations combined with molecular simulations to study the assembly of PCF，i.e. ① assembly of Metal Organic Frameworks (MOF) by clusters of metal ions with phthalocyanine or porphyrin ligands as organic linker, and ② assembly of Covalent Organic Frameworks (COF) by phthalocyanine or porphyrin ligands and organic molecules. Further modulations will be applied to PCF, including: ① introducing active metal sites to the center of phthalocyanine or porphyrin; ② introducing active substitutional group to phthalocyanine and porphyrin ligands since they both can be easily modulated; ③ doping metal atoms. The microcosmic mechanism of adsorption of carbon dioxide on PCF will be explored by our simulation, which can tell us how to promote the properties of PCF for carbon dioxide capture. The present project can help us to design PCF with high carbon dioxide capture efficiency. It can support some theoretical basis for experimental works.

多孔配位骨架(PCF)材料由于具有丰富的空间拓扑结构且结构可调，同时具有高比表面积和低密度等优点而成为极有前途的二氧化碳捕获材料。本课题将在我们现有理论工作[J.Chem.Phys.,136,234703(2012)]的基础上，采用第一性原理计算与分子模拟相结合的方法，研究以酞菁和卟啉化合物为配体的PCF材料的组装：①酞菁或卟啉配体作为有机连接体与金属团簇组装金属有机骨架材料；②酞菁或卟啉配体与有机分子组装共价有机骨架材料。进一步对其碳捕获性能进行调控：①在酞菁或卟啉的大环中心引入活性金属位点；②鉴于酞菁和卟啉的取代基易于进行化学修饰的特点，为其引入能够吸附二氧化碳的取代基；③掺杂金属原子。通过计算模拟揭示材料对二氧化碳吸附作用的微观机理，总结可以提升材料二氧化碳捕获性能的调控方式。本项目的开展有助于设计出具有高二氧化碳捕获性能的PCF材料，并为实验上可控合成提供理论依据和技术支撑。

本项目中，我们以酞菁和卟啉化合物为配体设计、组装多孔配位骨架（PCF）材料，包括以酞菁或卟啉配体作为有机连接体与金属团簇组装的金属有机骨架材料，以及酞菁或卟啉配体与有机连接组装的共价有机骨架材料。进一步尝试在酞菁或卟啉的大环中心引入活性金属位点，在酞菁和卟啉配体中引入能够吸附二氧化碳的取代基，掺杂金属原子等方法以提升其碳捕获性能，并通过第一性原理计算与巨正则蒙特卡洛模拟相结合的方法对材料的碳捕获性能进行了分析、验证。