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Title: An experimental and computational study of CO 2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

Abstract

We present a comprehensive investigation of the CO 2 adsorption properties of an isostructural series of metal-organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT 3-= 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO 2 adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO 2 binding sites, including CO 2 positions and orientations, as well as the experimentally determined isosteric heats of CO 2 adsorption.The work provides molecular level insight into the CO 2adsorption properties of an isostructural series of MOFs, known as M-BTT.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [7]; ORCiD logo [8]; ORCiD logo [1]
  1. Ecole Polytechnique Federale de Lausanne (EPFL), Sion (Switzerland)
  2. Ecole Polytechnique Federale de Lausanne (EPFL), Sion (Switzerland); Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Univ. of Delaware, Newark, DE (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  5. Chalk River Labs, Chalk River, ON (Canada)
  6. Univ. of South Dakota, Vermillion, SD (United States)
  7. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  8. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1435854
Alternate Identifier(s):
OSTI ID: 1465423
Grant/Contract Number:  
AC02-05CH11231; SC0001015
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 20; Related Information: © 2018 The Royal Society of Chemistry.; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., and Queen, Wendy L. An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites. United States: N. p., 2018. Web. doi:10.1039/c8sc00971f.
Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., & Queen, Wendy L. An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites. United States. doi:10.1039/c8sc00971f.
Asgari, Mehrdad, Jawahery, Sudi, Bloch, Eric D., Hudson, Matthew R., Flacau, Roxana, Vlaisavljevich, Bess, Long, Jeffrey R., Brown, Craig M., and Queen, Wendy L. Mon . "An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites". United States. doi:10.1039/c8sc00971f.
@article{osti_1435854,
title = {An experimental and computational study of CO2 adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites},
author = {Asgari, Mehrdad and Jawahery, Sudi and Bloch, Eric D. and Hudson, Matthew R. and Flacau, Roxana and Vlaisavljevich, Bess and Long, Jeffrey R. and Brown, Craig M. and Queen, Wendy L.},
abstractNote = {We present a comprehensive investigation of the CO2 adsorption properties of an isostructural series of metal-organic frameworks, M-BTT (M = Cr, Mn, Fe, Cu; BTT3-= 1,3,5-benzenetristetrazolate), which exhibit a high density of open metal sites capable of polarizing and binding guest molecules. Coupling gas adsorption measurements with in situ neutron and X-ray diffraction experiments provides molecular-level insight into the adsorption process and enables rationalization of the observed adsorption isotherms. In particular, structural data confirms that the high initial isosteric heats of CO2 adsorption for the series are directly correlated with the presence of open metal sites and further reveals the positions and orientations of as many as three additional adsorption sites. Density functional theory calculations that include van der Waals dispersion corrections quantitatively support the observed structural features associated with the primary and secondary CO2 binding sites, including CO2 positions and orientations, as well as the experimentally determined isosteric heats of CO2 adsorption.The work provides molecular level insight into the CO2adsorption properties of an isostructural series of MOFs, known as M-BTT.},
doi = {10.1039/c8sc00971f},
journal = {Chemical Science},
issn = {2041-6520},
number = 20,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c8sc00971f

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Cited by: 7 works
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Works referenced in this record:

Projector augmented-wave method
journal, December 1994


Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework
journal, October 2011

  • Gassensmith, Jeremiah J.; Furukawa, Hiroyasu; Smaldone, Ronald A.
  • Journal of the American Chemical Society, Vol. 133, Issue 39, p. 15312-15315
  • DOI: 10.1021/ja206525x

UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992

  • Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
  • Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
  • DOI: 10.1021/ja00051a040

M2(m-dobdc) (M = Mg, Mn, Fe, Co, Ni) Metal–Organic Frameworks Exhibiting Increased Charge Density and Enhanced H2 Binding at the Open Metal Sites
journal, August 2014

  • Kapelewski, Matthew T.; Geier, Stephen J.; Hudson, Matthew R.
  • Journal of the American Chemical Society, Vol. 136, Issue 34, p. 12119-12129
  • DOI: 10.1021/ja506230r

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Enhanced H2 Adsorption in Isostructural Metal−Organic Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions
journal, November 2008

  • Zhou, Wei; Wu, Hui; Yildirim, Taner
  • Journal of the American Chemical Society, Vol. 130, Issue 46, p. 15268-15269
  • DOI: 10.1021/ja807023q

Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

  • Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871
  • DOI: 10.1021/ja8036096

Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2
journal, June 2010

  • Murray, Leslie J.; Dinca, Mircea; Yano, Junko
  • Journal of the American Chemical Society, Vol. 132, Issue 23, p. 7856-7857
  • DOI: 10.1021/ja1027925

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units
journal, February 2005

  • Rosi, Nathaniel L.; Kim, Jaheon; Eddaoudi, Mohamed
  • Journal of the American Chemical Society, Vol. 127, Issue 5, p. 1504-1518
  • DOI: 10.1021/ja045123o

Hydrogen storage and carbon dioxide capture in an iron-based sodalite-type metal–organic framework (Fe-BTT) discovered via high-throughput methods
journal, January 2010

  • Sumida, Kenji; Horike, Satoshi; Kaye, Steven S.
  • Chemical Science, Vol. 1, Issue 2, p. 184-191
  • DOI: 10.1039/c0sc00179a

Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide
journal, January 2009

  • Dietzel, Pascal D. C.; Besikiotis, Vasileios; Blom, Richard
  • Journal of Materials Chemistry, Vol. 19, Issue 39, p. 7362-7370
  • DOI: 10.1039/b911242a

Impact of Metal and Anion Substitutions on the Hydrogen Storage Properties of M-BTT Metal–Organic Frameworks
journal, January 2013

  • Sumida, Kenji; Stück, David; Mino, Lorenzo
  • Journal of the American Chemical Society, Vol. 135, Issue 3, p. 1083-1091
  • DOI: 10.1021/ja310173e

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