一系列同构沸石咪唑骨架中二氧化碳捕获的联合实验-计算研究。
A combined experimental-computational investigation of carbon dioxide capture in a series of isoreticular zeolitic imidazolate frameworks.
机构信息
Center for Reticular Chemistry, Department of Chemistry and Biochemistry, University of California-Los Angeles, California 90095, USA.
出版信息
J Am Chem Soc. 2010 Aug 18;132(32):11006-8. doi: 10.1021/ja104035j.
A series of five zeolitic imidazolate frameworks (ZIFs) have been synthesized using zinc(II) acetate and five different 4,5-functionalized imidazole units, namely ZIF-25, -71, -93, -96, and -97. These 3-D porous frameworks have the same underlying topology (RHO) with Brunauer-Emmet-Teller surface areas ranging from 564 to 1110 m(2)/g. The only variation in structure arises from the functional groups that are directed into the pores of these materials, which include -CH(3), -OH, -Cl, -CN, -CHO, and -NH(2); therefore these 3-D frameworks are ideal for the study of the effect of functionality on CO(2) uptake. Experimental results show CO(2) uptake at approximately 800 Torr and 298 K ranging from 0.65 mmol g(-1) in ZIF-71 to 2.18 mmol g(-1) in ZIF-96. Molecular modeling calculations reproduce the pronounced dependence of the equilibrium adsorption on functionalization and suggest that polarizability and symmetry of the functionalization on the imidazolate are key factors leading to high CO(2) uptake.
已经合成了一系列五种沸石咪唑酯骨架（ZIF），使用的是乙酸锌和五种不同的 4,5-官能化咪唑单元，即 ZIF-25、-71、-93、-96 和-97。这些 3-D 多孔骨架具有相同的基本拓扑结构（RHO），比表面积范围从 564 到 1110 m(2)/g。结构上的唯一差异来自于定向到这些材料孔中的官能团，包括-CH(3)、-OH、-Cl、-CN、-CHO 和-NH(2)；因此，这些 3-D 骨架非常适合研究功能对 CO(2)吸收的影响。实验结果表明，在 800 Torr 和 298 K 下，CO(2)的吸收量从 ZIF-71 的 0.65 mmol g(-1)到 ZIF-96 的 2.18 mmol g(-1)不等。分子建模计算再现了平衡吸附对功能化的显著依赖性，并表明功能化在咪唑上的极化率和对称性是导致高 CO(2)吸收的关键因素。
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