Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality

Vsevolod A. Bolotov, Konstantin A. Kovalenko, Denis G. Samsonenko, Xue Han, Xinran Zhang, Gemma L. Smith, Laura J. M'Cormick, Simon J. Teat, Sihai Yang, Matthew J. Lennox, Alice Henley, Elena Besley, Vladimir P. Fedin, Danil N. Dybtsev, Martin Schroder

Research output: Contribution to journalArticlepeer-review

60 Downloads (Pure)

Abstract

The complex [Zn2(tdc)2dabco] (H2tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO2) uptake and CO2/dinitrogen (N2) selectivity compared to the nonthiophene analogue [Zn2(bdc)2dabco] (H2bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO2 adsorption at 1 bar for [Zn2(tdc)2dabco] is 67.4 cm3·g–1 (13.2 wt %) at 298 K and 153 cm3·g–1 (30.0 wt %) at 273 K. For [Zn2(bdc)2dabco], the equivalent values are 46 cm3·g–1 (9.0 wt %) and 122 cm3·g–1 (23.9 wt %), respectively. The isosteric heat of adsorption for CO2 in [Zn2(tdc)2dabco] at zero coverage is low (23.65 kJ·mol–1), ensuring facile regeneration of the porous material. Enhancement by the thiophene group on the separation of CO2/N2 gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO2 in [Zn2(tdc)2dabco] have been unambiguously determined by in situ single-crystal diffrac...
Original languageEnglish
Pages (from-to)5074-5082
Number of pages9
JournalInorganic Chemistry
Volume57
Issue number9
Early online date23 Apr 2018
DOIs
Publication statusPublished - 7 May 2018

Fingerprint

Dive into the research topics of 'Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality'. Together they form a unique fingerprint.

Cite this