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一种基于定制设计的二异酞酸配体的金属有机骨架,表现出优异的水稳定性和对 CH 和 CO 的高选择性吸附。

A metal-organic framework based on a custom-designed diisophthalate ligand exhibiting excellent hydrostability and highly selective adsorption of CH and CO over CH.

机构信息

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004, China.

出版信息

Dalton Trans. 2018 May 29;47(21):7213-7221. doi: 10.1039/c8dt00863a.

Abstract

The ligand truncation strategy provides facile access to a wide variety of linkers for the construction of MOFs bearing diverse structures and intriguing properties. In this work, we employed this strategy to design and prepare a novel bent diisophthalate ligand, and used it to successfully construct a copper-based MOF ZJNU-51 with the formula of [Cu2L(H2O)2]·5DMF (H4L = 5,5'-(triphenylamine-4,4'-diyl) diisophthalic acid), which was thoroughly characterized by various techniques including FTIR, TGA, PXRD and single-crystal X-ray diffraction. ZJNU-51 is a two-fold interpenetrated network in which the single network consists of dicopper paddlewheel units connected by the organic ligands and contains open channels as well as six distinct types of metal-organic cages. Furthermore, gas adsorption properties with respect to C2H2, CO2, and CH4 were systematically investigated, demonstrating that ZJNU-51 is a highly promising material for C2H2/CH4 and CO2/CH4 separations. Specifically, the IAST adsorption selectivity at 298 K and 1 atm reaches 35.6 and 5.4 for the equimolar C2H2/CH4 and CO2/CH4 gas mixtures, respectively. More significantly, as revealed by PXRD and N2 adsorption measurements, ZJNU-51 exhibits excellent chemical stability, which lays a good foundation for its practical application.

摘要

配体截断策略为构建具有各种结构和有趣性质的 MOF 提供了广泛的连接体。在这项工作中,我们采用了这种策略来设计和制备一种新型的弯曲二苯二甲酸配体,并成功地用它合成了一种铜基 MOF ZJNU-51,其化学式为[Cu2L(H2O)2]·5DMF(H4L=5,5'-(三苯胺-4,4'-二基)二苯二甲酸),通过各种技术对其进行了彻底的表征,包括 FTIR、TGA、PXRD 和单晶 X 射线衍射。ZJNU-51 是一个双重互穿网络,其中单网络由通过有机配体连接的双铜桨轮单元组成,包含开放通道和六种不同类型的金属-有机笼。此外,还系统地研究了其对 C2H2、CO2 和 CH4 的气体吸附性能,结果表明 ZJNU-51 是 C2H2/CH4 和 CO2/CH4 分离的很有前途的材料。具体而言,在 298 K 和 1 atm 下,等摩尔 C2H2/CH4 和 CO2/CH4 气体混合物的 IAST 吸附选择性分别达到 35.6 和 5.4。更重要的是,正如 PXRD 和 N2 吸附测量所揭示的那样,ZJNU-51 表现出优异的化学稳定性,为其实际应用奠定了良好的基础。

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