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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...
Autores principales: | , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2018
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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. |
format | Online Article Text |
id | pubmed-5951605 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
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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