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Revving Up a Designed Copper Catecholate Porous Organic Polymer for Its Potent Ethylene Adsorption than Ethane.

Authors :
Das N
Maibam A
Yun H
Boro B
Hong CS
Babarao R
Mondal J
Source :
Inorganic chemistry [Inorg Chem] 2024 Oct 21; Vol. 63 (42), pp. 19759-19768. Date of Electronic Publication: 2024 Oct 09.
Publication Year :
2024

Abstract

The potential to produce high-purity C <subscript>2</subscript> H <subscript>4</subscript> has made ethylene-selective adsorbents for ethane (C <subscript>2</subscript> H <subscript>6</subscript> )/ethylene (C <subscript>2</subscript> H <subscript>4</subscript> ) gas mixture separation appealing as viable substitutes for traditional cryogenic distillation. In this aspect, porous organic polymers (POPs) are anticipated to become the next-generation potential adsorbent due to their easily customizable functions and functional sites suitable for gas separation. This article reports the selective C <subscript>2</subscript> H <subscript>4</subscript> adsorption over C <subscript>2</subscript> H <subscript>6</subscript> using microporous copper(I)-coordinated POP ( Cu@Di-POP ) via fine-tuning of the π complexation and pore size. The specially designed adsorbent has the ideal pore size and coordinated Cu(I) ions to form π-complexation with C <subscript>2</subscript> H <subscript>4</subscript> molecules, which enabled it to adsorb C <subscript>2</subscript> H <subscript>4</subscript> (at 1 bar, 24.9, 18.9, and 13.4 cm <superscript>3</superscript> g <superscript>-1</superscript> at 273, 298, and 323 K, respectively) while significantly reducing C <subscript>2</subscript> H <subscript>6</subscript> adsorption (at 1 bar, 16.9, 12.7, and 8.8 cm <superscript>3</superscript> g <superscript>-1</superscript> at 273, 298, and 323 K, respectively). At 1 bar, Cu@Di-POP exhibited IAST selectivities of 6.09, 5.60, and 4.13 for C <subscript>2</subscript> H <subscript>4</subscript> /C <subscript>2</subscript> H <subscript>6</subscript> at 273, 298, and 323 K, respectively, suggesting its C <subscript>2</subscript> H <subscript>4</subscript> selective behavior, which was further confirmed from the experimental breakthrough measurement. Furthermore, the computational studies carried out with density functional theory highlighted an enhanced charge distribution leading to dπ-pπ conjugation between C <subscript>2</subscript> H <subscript>4</subscript> π-electrons and Cu d-electrons, thereby showing a relatively higher interaction energy of -37.23 kcal/mol with C <subscript>2</subscript> H <subscript>4</subscript> as compared to -16.06 kcal/mol with C <subscript>2</subscript> H <subscript>6</subscript> gas molecules.

Details

Language :
English
ISSN :
1520-510X
Volume :
63
Issue :
42
Database :
MEDLINE
Journal :
Inorganic chemistry
Publication Type :
Academic Journal
Accession number :
39382204
Full Text :
https://doi.org/10.1021/acs.inorgchem.4c02987