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

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

Journal

Nanomaterials
ISSN: 2079-4991

Output data

Year: 2022, Volume: 12, Number: 23, Article number : 4281, Pages count : 14 DOI: 10.3390/nano12234281

Authors

Dubskikh Vadim A. ¹ , Kovalenko Konstantin A. ¹ , Nizovtsev Anton S. ^1,2 , Lysova Anna A. ¹ , Samsonenko Denis G. ¹ , Dybtsev Danil N. ¹ , Fedin Vladimir P. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., Novosibirsk 630090, Russia
2	Novosibirsk State University, 2 Pirogov Street, Novosibirsk 630090, Russia

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.

Dubskikh V.A. , Kovalenko K.A. , Nizovtsev A.S. , Lysova A.A. , Samsonenko D.G. , Dybtsev D.N. , Fedin V.P.
Enhanced Adsorption Selectivity of Carbon Dioxide and Ethane on Porous Metal–Organic Framework Functionalized by a Sulfur-Rich Heterocycle
Nanomaterials. 2022. V.12. N23. 4281 :1-14. DOI: 10.3390/nano12234281 WOS Scopus OpenAlex

Submitted:	Oct 31, 2022
Accepted:	Nov 28, 2022
Published online:	Dec 1, 2022

Web of science:	WOS:000896177700001
Scopus:	2-s2.0-85143697038
OpenAlex:	W4311106116

DB	Citing
Web of science	8
Scopus	7
OpenAlex	10