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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

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:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
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
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
OSTI Identifier:
1465423

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., 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.. 2018. "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. https://www.osti.gov/servlets/purl/1465423.
@article{osti_1465423,
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},
number = 20,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

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