Enhanced Adsorption Selectivity of Carbon Dioxide and Ethane on Porous Metal-Organic Framework Functionalized by a Sulfur-Rich Heterocycle.

Content Provider	Europe PMC
Author	Dubskikh, Vadim A. Kovalenko, Konstantin A. Nizovtsev, Anton S. Lysova, Anna A. Samsonenko, Denis G. Dybtsev, Danil N. Fedin, Vladimir P.
Editor	Vilardi, Giorgio
Copyright Year	2022
Abstract	Porous metal–organic framework [Zn2(ttdc)2(bpy)] (1) based on thieno [3,2-b]thiophenedicarboxylate (ttdc) was synthesized and characterized. The structure contains intersected zig-zag channels with an average aperture of 4 × 6 Å and a 49% (v/v) guest-accessible pore volume. Gas adsorption studies confirmed the microporous nature of 1 with a specific surface area (BET model) of 952 m2·g–1 and a pore volume of 0.37 cm3·g–1. Extensive CO2, N2, O2, CO, CH4, C2H2, C2H4 and C2H6 gas adsorption experiments at 273 K and 298 K were carried out, which revealed the great adsorption selectivity of C2H6 over CH4 (IAST selectivity factor 14.8 at 298 K). The sulfur-rich ligands and double framework interpenetration in 1 result in a dense decoration of the inner surface by thiophene heterocyclic moieties, which are known to be effective secondary adsorption sites for carbon dioxide. As a result, remarkable CO2 adsorption selectivities were obtained for CO2/CH4 (11.7) and CO2/N2 (27.2 for CO2:N2 = 1:1, 56.4 for CO2:N2 = 15:85 gas mixtures). The computational DFT calculations revealed the decisive role of the sulfur-containing heterocycle moieties in the adsorption of CO2 and C2H6. High CO2 adsorption selectivity values and a relatively low isosteric heat of CO2 adsorption (31.4 kJ·mol–1) make the porous material 1 a promising candidate for practical separation of biogas as well as for CO2 sequestration from flue gas or natural gas.
Journal	Nanomaterials (Basel, Switzerland)
Volume Number	12
PubMed Central reference number	PMC9737143
Issue Number	23
PubMed reference number	36500905
e-ISSN	20794991
DOI	10.3390/nano12234281
Language	English
Publisher	MDPI
Publisher Date	2022-12-01
Access Restriction	Open
Rights License	Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). © 2022 by the authors.
Subject Keyword	metal–organic framework thieno[3,2-b]thiophenedicarboxylic acid gas adsorption adsorption selectivity benzene and cyclohexane separation
Content Type	Text
Resource Type	Article
Subject	Chemical Engineering Materials Science