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Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality

[Image: see text] The complex [Zn(2)(tdc)(2)dabco] (H(2)tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO(2)) uptake and CO(2)/dinitrogen (N(2)) selectivity compared to the nonthiophene analogue [Zn(2)(bdc)(2)dabco] (H(2)bdc = be...

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Autores principales: 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., Schröder, Martin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5951605/
https://www.ncbi.nlm.nih.gov/pubmed/29683657
http://dx.doi.org/10.1021/acs.inorgchem.8b00138
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author 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.
Schröder, Martin
author_facet 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.
Schröder, Martin
author_sort Bolotov, Vsevolod A.
collection PubMed
description [Image: see text] The complex [Zn(2)(tdc)(2)dabco] (H(2)tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO(2)) uptake and CO(2)/dinitrogen (N(2)) selectivity compared to the nonthiophene analogue [Zn(2)(bdc)(2)dabco] (H(2)bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO(2) adsorption at 1 bar for [Zn(2)(tdc)(2)dabco] is 67.4 cm(3)·g(–1) (13.2 wt %) at 298 K and 153 cm(3)·g(–1) (30.0 wt %) at 273 K. For [Zn(2)(bdc)(2)dabco], the equivalent values are 46 cm(3)·g(–1) (9.0 wt %) and 122 cm(3)·g(–1) (23.9 wt %), respectively. The isosteric heat of adsorption for CO(2) in [Zn(2)(tdc)(2)dabco] 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 CO(2)/N(2) gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO(2) in [Zn(2)(tdc)(2)dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO(2)-loaded [Zn(2)(tdc)(2)dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO(2) binding via an induced dipole interaction between CO(2) and the sulfur center, confirming that an enhanced CO(2) capacity in [Zn(2)(tdc)(2)dabco] 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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spelling pubmed-59516052018-05-15 Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality 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. Schröder, Martin Inorg Chem [Image: see text] The complex [Zn(2)(tdc)(2)dabco] (H(2)tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO(2)) uptake and CO(2)/dinitrogen (N(2)) selectivity compared to the nonthiophene analogue [Zn(2)(bdc)(2)dabco] (H(2)bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO(2) adsorption at 1 bar for [Zn(2)(tdc)(2)dabco] is 67.4 cm(3)·g(–1) (13.2 wt %) at 298 K and 153 cm(3)·g(–1) (30.0 wt %) at 273 K. For [Zn(2)(bdc)(2)dabco], the equivalent values are 46 cm(3)·g(–1) (9.0 wt %) and 122 cm(3)·g(–1) (23.9 wt %), respectively. The isosteric heat of adsorption for CO(2) in [Zn(2)(tdc)(2)dabco] 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 CO(2)/N(2) gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO(2) in [Zn(2)(tdc)(2)dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO(2)-loaded [Zn(2)(tdc)(2)dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO(2) binding via an induced dipole interaction between CO(2) and the sulfur center, confirming that an enhanced CO(2) capacity in [Zn(2)(tdc)(2)dabco] 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. American Chemical Society 2018-04-23 2018-05-07 /pmc/articles/PMC5951605/ /pubmed/29683657 http://dx.doi.org/10.1021/acs.inorgchem.8b00138 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle 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.
Schröder, Martin
Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title_full Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title_fullStr Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title_full_unstemmed Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title_short Enhancement of CO(2) Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality
title_sort enhancement of co(2) uptake and selectivity in a metal–organic framework by the incorporation of thiophene functionality
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5951605/
https://www.ncbi.nlm.nih.gov/pubmed/29683657
http://dx.doi.org/10.1021/acs.inorgchem.8b00138
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