Design of Pore Size and Functionality in Pillar-Layered Zn-Triazolate-Dicarboxylate Frameworks and Their High CO2/CH4 and C2 Hydrocarbons/CH4 Selectivity

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• 作者：Quan-Guo Zhai ; Ni Bai ; Shu鈥檔i Li ; Xianhui Bu ; Pingyun Feng
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 19, 2015
• 年：2015
• 卷：54
• 期：20
• 页码：9862-9868
• 全文大小：573K
• ISSN：1520-510X

文摘

In the design of new materials, those with rare and exceptional compositional and structural features are often highly valued and sought after. On the other hand, materials with common and more accessible modes can often provide richer and unsurpassed compositional and structural variety that makes them a more suitable platform for systematically probing the composition鈥搒tructure鈥損roperty correlation. We focus here on one such class of materials, pillar-layered metal鈥搊rganic frameworks (MOFs), because different pore size and shape as well as functionality can be controlled and adjusted by using pillars with different geometrical and chemical features. Our approach takes advantage of the readily accessible layered Zn-1,2,4-triazolate motif and diverse dicarboxylate ligands with variable length and functional groups, to prepare seven Zn-triazolate-dicarboxylate pillar-layered MOFs. Six different gases (N₂, H₂, CO₂, C₂H₂, C₂H₄, and CH₄) were used to systematically examine the dependency of gas sorption properties on chemical and geometrical properties of those MOFs as well as their potential applications in gas storage and separation. All of these pillar-layered MOFs show not only remarkable CO₂ uptake capacity, but also high CO₂ over CH₄ and C2 hydrocarbons over CH₄ selectivity. An interesting observation is that the BDC ligand (BDC = benzenedicarboxylate) led to a material with the CO₂ uptake outperforming all other metal-triazolate-dicarboxylate MOFs, even though most of them are decorated with amino groups, generally believed to be a key factor for high CO₂ uptake. Overall, the data show that the exploration of the synergistic effect resulting from combined tuning of functional groups and pore size may be a promising strategy to develop materials with the optimum integration of geometrical and chemical factors for the highest possible gas adsorption capacity and separation performance.