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

The complex [Zn 2(tdc) 2dabco] (H 2tdc = 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) 2dabco] (H 2bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO 2 adsorption at 1 bar for [Zn 2(tdc) 2dabco] 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) 2dabco], 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) 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 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) 2dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO 2-loaded [Zn 2(tdc) 2dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO 2 binding via anmore » induced dipole interaction between CO 2 and the sulfur center, confirming that an enhanced CO 2 capacity in [Zn 2(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.« less
Authors:
 [1] ;  [2] ;  [2] ;  [3] ;  [3] ;  [3] ; ORCiD logo [4] ;  [4] ;  [3] ;  [5] ;  [6] ; ORCiD logo [6] ;  [2] ;  [2] ; ORCiD logo [7]
  1. Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation)
  2. Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation); Novosibirsk State Univ., Novosibirsk (Russian Federation)
  3. Univ. of Manchester, Manchester (United Kingdom)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Univ. of Bath, Bath (United Kingdom); Univ. of Nottingham, Nottingham (United Kingdom)
  6. Univ. of Nottingham, Nottingham (United Kingdom)
  7. Siberian Branch of the Russian Academy of Sciences, Novosibirsk (Russian Federation); Univ. of Manchester, Manchester (United Kingdom)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 9; Related Information: © 2018 American Chemical Society.; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Carbon dioxide; metal-organic framework; thiophene; carboxylate; zinc; binding site; breakthrough
OSTI Identifier:
1460318

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., and Schroder, Martin. Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality. United States: N. p., Web. doi: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., & Schroder, Martin. Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality. United States. doi: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., and Schroder, Martin. 2018. "Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality". United States. doi:10.1021/acs.inorgchem.8b00138. https://www.osti.gov/servlets/purl/1460318.
@article{osti_1460318,
title = {Enhancement of CO2 Uptake and Selectivity in a Metal–Organic Framework by the Incorporation of Thiophene Functionality},
author = {Bolotov, Vsevolod A. and Kovalenko, Konstantin A. and Samsonenko, Denis G. and Han, Xue and Zhang, Xinran and Smith, Gemma L. and MCormick, Laura J. and Teat, Simon J. and Yang, Sihai and Lennox, Matthew J. and Henley, Alice and Besley, Elena and Fedin, Vladimir P. and Dybtsev, Danil N. and Schroder, Martin},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.8b00138},
journal = {Inorganic Chemistry},
number = 9,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}