Issue 32, 2019

Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks

Abstract

The structure–property relationship investigation is of prime importance to development of porous MOFs exhibiting better performance. In this work, two regioisomeric diisophthalate ligands, with the only difference being the position of methyl and amino groups with respect to isophthalate moieties, were rationally designed and synthesized, and their corresponding dicopper paddlewheel-based MOFs were successfully fabricated under suitable solvothermal conditions. Single-crystal X-ray diffraction studies showed that they displayed the same network topology of ssa type, thus providing a platform to investigate the impact of the substituent's arrangement on gas adsorption properties. As revealed by gas adsorption studies, the pore textural properties and gas uptake capacities with respect to C2H2, CO2, and CH4 of ZJNU-11 are significantly higher than those of its isomer ZJNU-12 despite their same structures, indicating that the arrangement of functional groups makes a difference to the framework stabilities against desolvation and thus to the gas adsorption properties. In addition, ZJNU-11 is also capable of selectively adsorptive separation of C2H2 and CO2 from CH4, with high C2H2/CH4 (v/v, 1/1) and CO2/CH4 (v/v, 1/1) adsorption selectivities of 36.2 and 5.9 at 298 K and 1 atm. This work not only reported a porous MOF material for highly selective C2H2/CH4 and CO2/CH4 separations, but also demonstrated that the rational arrangement of substituent groups will be favorable to improve the MOF's stabilities and thus gas adsorption properties, which needs to be taken into account upon design and construction of porous MOFs.

Graphical abstract: Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks

Supplementary files

Article information

Article type
Paper
Submitted
08 Jun 2019
Accepted
10 Jul 2019
First published
10 Jul 2019

CrystEngComm, 2019,21, 4820-4827

Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks

T. Xu, Z. Jiang, M. He, X. Gao and Y. He, CrystEngComm, 2019, 21, 4820 DOI: 10.1039/C9CE00882A

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