【作者】 王倩；

【导师】 白俊峰；

【作者基本信息】 南京大学 ， 无机化学， 2016， 博士

【摘要】 严峻的气候变化迫使人们不断寻求缓解人为向大气中排放二氧化碳的方法。目前,可采用的方案有捕获烟道气CO2和近期广泛使用天然气。由于结构的多样性、可设计性和调控性,金属-有机骨架材料(MOFs)作为一种晶态多孔固体材料,在气体吸附、分离方面有着广泛的应用前景。但是,在烟道气CO2捕获和天然气储存方面,对MOFs的研究仍然存在着:(1)系统研究的MOF体系较少,无裸露金属位点的MOF体系研究更少;(2)针对特定MOF体系研究刚刚开始。本论文利用5-(氮杂芳环-n-基)间苯二羧酸的有机配体(LA-LG)和Cu桨轮单元构筑了一系列不含裸露金属位点的柱层MOFs 1-7,较系统地研究了有机配体中取代基的修饰和配体延长对MOFs拓扑结构的影响,并初步研究了它们的CO2的选择性吸附或CH4储存性能:1、rtl-MOF:在MOF 1和2中,有机配体中“支柱部分”的-Cl,-CH3修饰和5-喹啉取代4-吡啶成功调控它们的孔径至合适尺寸:3.4 A(1),3.6 A(2)。2具有较高的水/热稳定性。2展现出了较高的CO2/N2吸附选择性。2还表现出较好的多轮吸附行为和较迅速的动力学吸附。2、pyr-MOF:在MOF3中,有机配体中“支柱部分”的较大空间位阻的6-喹啉取代4-吡啶成功导致了 pyr-MOF 3的合成,这是第二例具有pyr拓扑的MOF。3、eea-MOF:在MOF 4-7中,较长的有机配体LD、LE、LF和LG和Cu的使用成功制备了一系列eea-MOF 4-7。含有较长配体的5相对于4具有更高的多孔性和比表面积。-NH2修饰的6和4-喹啉取代的7的密度、孔体积、孔径均与5的稍有不同。高压下,5具有最高的甲烷储存量:182 cm3/cm3。更多还原

【Abstract】 Climate change has compelled people to seek the solution of decreasing the anthropic CO2 emmission in the air.Currently,two promising approaches may be CO2 capture from the flue gas and nature gas utilization.Due to their structural diversity and fine-tunablity and framework designability,metal-organic frameworks(MOFs),as one new kind of crystalline porous solid materials,have great potential applications in gas storage and separation.Nevertheless,there still are some problems to be solved in both CO2 capture from the flue gas and nature gas storage:(1)MOFs series for systematically exploring both of them are less,and MOFs series without open metal sites for that are also much less;(2)the systematically investigation for both of them aiming at special MOF series are also just beginning.In this dissertation,we ultilizes 5-(nitrogen heterocyclic-n-yl)isophthalate(LA-LG)and Cu paddle-wheel to construct a series of pillar-layer MOFs without open metal sites and investigate the impacts of functional group attachment or ligand enlongation of organic ligands on the structures of MOFs.Furthermore,their CO2 selective adsorption and CH4 storage properties have initially investigated:1.By the attachment of both-Cl and-CH3 functional groups and the substitution of the quinolin-5-yl toward pyridin-4-yl in the "pillar" part of the organic ligand,MOF 1 and 2 were afforded with rtl topology,inducing the tuning of their pore sizes to the suitable sizes,3.4 A(1)and 3.6 A(2).Intereingly,MOF 2 possesses the high thermal/water stability,a high CO2/N2 adsorption selectivity,a good cyclic CO2 adsorption and a fast kinetic CO2 adsorption behavior.2.By the substitution of the larger quinolin-6-yl toward pyridin-4-yl in the "pillar"part of the organic ligand,MOF 3 was obtained with pyr topology,which was the second pyr topological MOF.3.By extending this type organic ligands longer,LD,LE,LF and LG,MOF 4-7 were afforded with eea topology.With the longer organic ligand,5 possesses the higher porosity than that of 4.By the attachment of-NH2 group and the quinolin-4-yl substituting pyridin-4-yl,the framework density,pore volume,pore size of 6 and 7 are all slightly different from those of 5.At the high pressure,5 possesses the highest total volumetric CH4 adsorption uptake,182 cm3/cm3(STP),among MOF 4-7.更多还原