Issue 39, 2018

Direct synthesis of an aliphatic amine functionalized metal–organic framework for efficient CO2 removal and CH4 purification

Abstract

Porous materials bearing free aliphatic amine groups are powerful adsorbents for carbon dioxide but generally have to be synthesized by complicated, multi-step post-synthetic modification methods due to the high activity of these functional groups. We report a crystal-engineering strategy for such metal–organic frameworks. Reactions of Zn(II) ion with diversified coordination modes and bis(4-carboxy-benzyl)amine (H2bcba) with a secondary aliphatic amine bridge at different temperatures yielded a pair of isomeric frameworks with very similar framework structures but distinctly different local structures, namely α-[Zn(bcba)] (MCF-51 or α-Zn) with all amino groups coordinated and β-[Zn(bcba)] (MCF-52 or β-Zn) with uncoordinated amino groups. Single-component gas adsorption and CO2/CH4 mixture breakthrough experiments at ambient conditions showed that, the CO2 adsorption ability and CH4 purification performances of β-Zn, in terms of CO2 adsorption enthalpy (42 kJ mol−1), CO2/CH4 selectivity (32) and CH4 purity/productivity (1.49 mmol g−1 at 99.999%+), are much higher than those of α-Zn (CO2 adsorption enthalpy of 17 kJ mol−1, CO2/CH4 selectivity of 2.9 and CH4 purity/productivity of 0.088 mmol g−1 at 99%+).

Graphical abstract: Direct synthesis of an aliphatic amine functionalized metal–organic framework for efficient CO2 removal and CH4 purification

Supplementary files

Article information

Article type
Paper
Submitted
11 4月 2018
Accepted
16 5月 2018
First published
17 5月 2018

CrystEngComm, 2018,20, 5969-5975

Direct synthesis of an aliphatic amine functionalized metal–organic framework for efficient CO2 removal and CH4 purification

N. Huang, Z. Mo, L. Li, W. Xu, H. Zhou, D. Zhou, P. Liao, J. Zhang and X. Chen, CrystEngComm, 2018, 20, 5969 DOI: 10.1039/C8CE00574E

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