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Enhancement of CO2 uptake and selectivity in a metal-organic framework by the incorporation of thiophene functionality

Enhancement of CO2 uptake and selectivity in a metal-organic framework by the incorporation of thiophene functionality
Enhancement of CO2 uptake and selectivity in a metal-organic framework by the incorporation of thiophene functionality

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 diffraction studies on CO2-loaded [Zn2(tdc)2dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO2 binding via an induced dipole interaction between CO2 and the sulfur center, confirming that an enhanced CO2 capacity in [Zn2(tdc)2dabco] is achieved without the presence of open metal sites. The experimental data and theoretical insight suggest a viable strategy for improvement of the adsorption properties of already known materials through the incorporation of sulfur-based heterocycles within their porous structures.

0020-1669
5074-5082
Bolotov, Vsevolod A.
2a482791-b3b0-40ee-b772-cc3c2c66362c
Kovalenko, Konstantin A.
2f5a148c-5066-4f25-9f1f-15100d02d7ba
Samsonenko, Denis G.
c54a0b0a-37a2-4126-b965-0cbb3b8fc8ec
Han, Xue
6fe07b0a-df76-4bc4-b9b7-8b3b4bbad3ab
Zhang, Xinran
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Smith, Gemma L.
939bcbd4-9cda-4ce5-9635-750d0c3618eb
McCormick, Laura J.
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Teat, Simon J.
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Yang, Sihai
2b65fe19-0e5a-454a-a135-d2f13fabad79
Lennox, Matthew J.
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Henley, Alice
9006916b-f325-4caf-9e67-bc533f772177
Besley, Elena
9628c33a-d2e2-478c-b357-b9eee8f31ba8
Fedin, Vladimir P.
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Dybtsev, Danil N.
dbf42d77-d2c1-4bd4-8a76-93918c3cf3d4
Schröder, Martin
467922b1-a6f5-45e0-b0b8-95f3cf76c2d5
Bolotov, Vsevolod A.
2a482791-b3b0-40ee-b772-cc3c2c66362c
Kovalenko, Konstantin A.
2f5a148c-5066-4f25-9f1f-15100d02d7ba
Samsonenko, Denis G.
c54a0b0a-37a2-4126-b965-0cbb3b8fc8ec
Han, Xue
6fe07b0a-df76-4bc4-b9b7-8b3b4bbad3ab
Zhang, Xinran
67276c76-1d6d-4b1c-80ab-45b1856caea5
Smith, Gemma L.
939bcbd4-9cda-4ce5-9635-750d0c3618eb
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Teat, Simon J.
fd6e6d90-b0c2-4463-91d2-5c72e212d414
Yang, Sihai
2b65fe19-0e5a-454a-a135-d2f13fabad79
Lennox, Matthew J.
b39af92b-1b61-4786-88ba-a28926f58c7c
Henley, Alice
9006916b-f325-4caf-9e67-bc533f772177
Besley, Elena
9628c33a-d2e2-478c-b357-b9eee8f31ba8
Fedin, Vladimir P.
7e62abf5-f4c6-44bc-a39c-fb7873214945
Dybtsev, Danil N.
dbf42d77-d2c1-4bd4-8a76-93918c3cf3d4
Schröder, Martin
467922b1-a6f5-45e0-b0b8-95f3cf76c2d5

Bolotov, Vsevolod A., Kovalenko, Konstantin A., Samsonenko, Denis G., Han, Xue, Zhang, Xinran, Smith, Gemma L., McCormick, Laura J., Teat, Simon J., Yang, Sihai, Lennox, Matthew J., Henley, Alice, Besley, Elena, Fedin, Vladimir P., Dybtsev, Danil N. and Schröder, Martin (2018) Enhancement of CO2 uptake and selectivity in a metal-organic framework by the incorporation of thiophene functionality. Inorganic Chemistry, 57 (9), 5074-5082. (doi:10.1021/acs.inorgchem.8b00138).

Record type: Article

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 diffraction studies on CO2-loaded [Zn2(tdc)2dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO2 binding via an induced dipole interaction between CO2 and the sulfur center, confirming that an enhanced CO2 capacity in [Zn2(tdc)2dabco] is achieved without the presence of open metal sites. The experimental data and theoretical insight suggest a viable strategy for improvement of the adsorption properties of already known materials through the incorporation of sulfur-based heterocycles within their porous structures.

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e-pub ahead of print date: 23 April 2018
Published date: 7 May 2018

Identifiers

Local EPrints ID: 438686
URI: http://eprints.soton.ac.uk/id/eprint/438686
ISSN: 0020-1669
PURE UUID: 9b54d4a7-8c15-40d6-850c-ca3e56b800a8
ORCID for Laura J. McCormick: ORCID iD orcid.org/0000-0002-6634-4717

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Date deposited: 20 Mar 2020 17:37
Last modified: 26 Nov 2021 03:21

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Contributors

Author: Vsevolod A. Bolotov
Author: Konstantin A. Kovalenko
Author: Denis G. Samsonenko
Author: Xue Han
Author: Xinran Zhang
Author: Gemma L. Smith
Author: Simon J. Teat
Author: Sihai Yang
Author: Matthew J. Lennox
Author: Alice Henley
Author: Elena Besley
Author: Vladimir P. Fedin
Author: Danil N. Dybtsev
Author: Martin Schröder

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