功能金属有机框架的吸附位优化及其CH4-N2分离机理

项目名称： 功能金属有机框架的吸附位优化及其CH4-N2分离机理

项目编号： No.21476231

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 有机化学

项目作者： 孙天军

作者单位： 中国科学院大连化学物理研究所

项目金额： 80万元

中文摘要： 甲烷与氮气的高效吸附分离是我国天然气资源与发展战略所面临的科学难题之一。相对于传统吸附剂，金属有机框架（MOF）不仅微孔有序发达，且具有表面结构与势能可控的优势，是甲烷氮气分离的优选吸附材料。本课题将利用'甲烷亲和性'有机物种或金属纳米团簇/颗粒对MOF材料的孔道进行修饰，优化吸附位点的物化性质，以强化其甲烷吸附性能，研究功能MOF材料强化甲烷氮气分离性能的机理。首先进行多孔MOF材料的吸附位点优化合成研究，掌握不同表面结构MOF材料的制备规律；然后进行功能MOF材料的甲烷氮气分离选择性、吸附量、吸附热力学与动力学性能评价，掌握修饰物种、微孔结构以及制备方法对吸附剂性能的影响规律；最终结合甲烷与氮气的原位吸附表征与吸附模拟计算结果，阐明MOF材料的吸附位点优化原理，及其甲烷氮气在功能MOF材料中的分离机理。通过本课题研究，将为甲烷氮气的高效分离提供一类功能MOF吸附剂设计制备的理论依据。

中文关键词： 甲烷；氮气；吸附分离；金属有机框架；机理

英文摘要： The adsorptive separation of CH4-N2 mixtures with high-efficiency, is one of the key scientific problems facing China on natural gas soures and the development strategy. Compared with conventional adsorbents, metal-organic frameworks (MOFs) will be the optimal adsorbents for the separation of CH4-N2 mixtures owing to their high porosity, well-defined pore sizes, and adjustable pore surface properties. In this study, one kind of novel MOF adsorbents will be optimized by a versatile chemical assembly method, in which the adsorption sites are modified by the functional organic radicals/moleculars or metal nano-clusters/paticles with CH4 affinity. These functional MOFs with novel adsortion sites are employed to enhance the adsorption of CH4, and the separation mechanism of CH4-N2 mixtures on these functional MOF adsorbents will be studied systematically. Firstly, the most suitable fabrication process of functional MOF adsorbents with optimized surface structures, will be developed via the systematic investigation of the preparation parameters. Subsequently, structural properties, the adsorption capacity and selectivity, thermal effect and dynamics of the separation of CH4-N2 mixtures will be investigated by the characterization and performance evaluation of the functional MOF adsorbents. And then, the rational relationship between separation performances and micro-structures of functional MOF adsorbents can be deduced accoroding to above-mentioned reasearches, in which the effect of functional radicals/moleculars, pore sizes, metal nanoclusters/particles and the preparation methods are considered thoroughly. Finally, combined the resunlt of in-situ characterization and simulation calculation of CH4-N2 adsorption, the mechanism that the separation peformence of CH4-N2 mixtures is enhanced on the functional MOF adsorbents, will be clarified. In a word, the findings of this research will offer a new theory for the design and preparation of a kind of functinal MOF adsorbents, which will overcome the bottleneck of the high-efficient separation of CH4-N2 mixtures.

英文关键词： Methane;Nitrogen;Adsorptive separation;Metal-organic frameworks;Mechanism