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. M'Cormick; Simon J. Teat; Sihai Yang; Matthew J. Lennox; Alice Henley; Elena Besley; Vladimir P. Fedin; Danil N. Dybtsev; Martin Schroder

doi:10.1021/acs.inorgchem.8b00138

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. M'Cormick, Simon J. Teat, Sihai Yang, Matthew J. Lennox, Alice Henley, Elena Besley, Vladimir P. Fedin, Danil N. Dybtsev, Martin Schroder

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

97 Downloads (Pure)

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 diffrac...

Original language	English
Pages (from-to)	5074-5082
Number of pages	9
Journal	Inorganic Chemistry
Volume	57
Issue number	9
Early online date	23 Apr 2018
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00138
Publication status	Published - 7 May 2018

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acs.inorgchem.8b00138

acs.inorgchem.8b00138Final published version, 6.43 MBLicence: CC BY

CCDC 1568885: Experimental Crystal Structure Determination
Bolotov, V. (Contributor), Kovalenko, K. (Contributor), Samsonenko, D. (Contributor), Han, X. (Contributor), Zhang, X. (Contributor), Smith, G. (Contributor), McCormick, L. (Contributor), Teat, S. J. (Contributor), Yang, S. (Contributor), Lennox , M. (Contributor), Henley, A. (Contributor), Besley, E. (Contributor), Fedin, V. P. (Contributor), Dybtsev, D. N. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1pnk63, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1pnk63&sid=DataCite
Dataset
CCDC 1503063: Experimental Crystal Structure Determination
Bolotov, V. (Contributor), Kovalenko, K. (Contributor), Samsonenko, D. (Contributor), Han, X. (Contributor), Zhang, X. (Contributor), Smith, G. (Contributor), McCormick, L. (Contributor), Teat, S. J. (Contributor), Yang, S. (Contributor), Lennox , M. (Contributor), Henley, A. (Contributor), Besley, E. (Contributor), Fedin, V. P. (Contributor), Dybtsev, D. N. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1mg1x1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mg1x1&sid=DataCite
Dataset
CCDC 1503065: Experimental Crystal Structure Determination
Bolotov, V. (Contributor), Kovalenko, K. (Contributor), Samsonenko, D. (Contributor), Han, X. (Contributor), Zhang, X. (Contributor), Smith, G. (Contributor), McCormick, L. (Contributor), Teat, S. J. (Contributor), Yang, S. (Contributor), Lennox , M. (Contributor), Henley, A. (Contributor), Besley, E. (Contributor), Fedin, V. P. (Contributor), Dybtsev, D. N. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1mg1z3, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mg1z3&sid=DataCite
Dataset

Cite this

Bolotov, V. A., Kovalenko, K. A., Samsonenko, D. G., Han, X., Zhang, X., Smith, G. L., M'Cormick, L. J., Teat, S. J., Yang, S., Lennox, M. J., Henley, A., Besley, E., Fedin, V. P., Dybtsev, D. N., & Schroder, 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

@article{646f3db9c43f42f0a39c36e98ba0d415,

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 diffrac...",

author = "Bolotov, {Vsevolod A.} and Kovalenko, {Konstantin A.} and Samsonenko, {Denis G.} and Xue Han and Xinran Zhang and Smith, {Gemma L.} and M'Cormick, {Laura J.} and Teat, {Simon J.} and Sihai Yang and Lennox, {Matthew J.} and Alice Henley and Elena Besley and Fedin, {Vladimir P.} and Dybtsev, {Danil N.} and Martin Schroder",

year = "2018",

month = may,

day = "7",

doi = "10.1021/acs.inorgchem.8b00138",

language = "English",

volume = "57",

pages = "5074--5082",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "9",

}

Bolotov, VA, Kovalenko, KA, Samsonenko, DG, Han, X, Zhang, X, Smith, GL, M'Cormick, LJ, Teat, SJ, Yang, S, Lennox, MJ, Henley, A, Besley, E, Fedin, VP, Dybtsev, DN & Schroder, 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

TY - JOUR

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 - M'Cormick, 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 - Schroder, 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 diffrac...

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 diffrac...

U2 - 10.1021/acs.inorgchem.8b00138

DO - 10.1021/acs.inorgchem.8b00138

M3 - Article

C2 - 29683657

SN - 0020-1669

VL - 57

SP - 5074

EP - 5082

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 9

ER -

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

Abstract

UN SDGs

Access to Document

Fingerprint

Datasets

CCDC 1568885: Experimental Crystal Structure Determination

CCDC 1503063: Experimental Crystal Structure Determination

CCDC 1503065: Experimental Crystal Structure Determination

Cite this