Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality

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

Research output: Contribution to journalArticle

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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.
Original languageEnglish
Pages (from-to)5074-5082
Number of pages9
JournalInorganic Chemistry
Volume57
Issue number9
Early online date23 Apr 2018
DOIs
Publication statusPublished - 7 May 2018

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Thiophenes
Carbon Monoxide
thiophenes
dicarboxylic acids
selectivity
Metals
adsorption
augmentation
sulfur
metals
porous materials
regeneration
gas mixtures
carbon dioxide
Dicarboxylic Acids
benzene
analogs
dipoles
heat
acids

Cite this

Bolotov, V. A., Kovalenko, K. A., Samsonenko, D. G., Han, X., Zhang, X., Smith, G. L., ... Schröder, M. (2018). Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality. Inorganic Chemistry, 57(9), 5074-5082. https://doi.org/10.1021/acs.inorgchem.8b00138

Enhancement of CO2 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.; Mcormick, Laura J.; Teat, Simon J.; Yang, Sihai; Lennox, Matthew J.; Henley, Alice; Besley, Elena; Fedin, Vladimir P.; Dybtsev, Danil N.; Schröder, Martin.

In: Inorganic Chemistry, Vol. 57, No. 9, 07.05.2018, p. 5074-5082.

Research output: Contribution to journalArticle

Bolotov, VA, Kovalenko, KA, Samsonenko, DG, Han, X, Zhang, X, Smith, GL, Mcormick, LJ, Teat, SJ, Yang, S, Lennox, MJ, Henley, A, Besley, E, Fedin, VP, Dybtsev, DN & Schröder, M 2018, 'Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality', Inorganic Chemistry, vol. 57, no. 9, pp. 5074-5082. https://doi.org/10.1021/acs.inorgchem.8b00138
Bolotov, Vsevolod A. ; Kovalenko, Konstantin A. ; Samsonenko, Denis G. ; Han, Xue ; Zhang, Xinran ; Smith, Gemma L. ; Mcormick, Laura J. ; Teat, Simon J. ; Yang, Sihai ; Lennox, Matthew J. ; Henley, Alice ; Besley, Elena ; Fedin, Vladimir P. ; Dybtsev, Danil N. ; Schröder, Martin. / Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 9. pp. 5074-5082.
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title = "Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality",
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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T1 - Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality

AU - Bolotov, Vsevolod A.

AU - Kovalenko, Konstantin A.

AU - Samsonenko, Denis G.

AU - Han, Xue

AU - Zhang, Xinran

AU - Smith, Gemma L.

AU - Mcormick, Laura J.

AU - Teat, Simon J.

AU - Yang, Sihai

AU - Lennox, Matthew J.

AU - Henley, Alice

AU - Besley, Elena

AU - Fedin, Vladimir P.

AU - Dybtsev, Danil N.

AU - Schröder, Martin

PY - 2018/5/7

Y1 - 2018/5/7

N2 - 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.

AB - 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.

U2 - 10.1021/acs.inorgchem.8b00138

DO - 10.1021/acs.inorgchem.8b00138

M3 - Article

VL - 57

SP - 5074

EP - 5082

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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