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Title: Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)

Abstract

Analysis of the CO₂ adsorption properties of a well-known series of metal–organic frameworks M₂(dobdc) (dobdc⁴⁻ = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO₂ adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO₂ within many of these materials while systematically varying both the amount of CO₂ and the temperature. Unlike previous studies, we show that CO₂ adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO₂ adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO₂. For the weaker CO₂ adsorbents, significant elongation of the metal–O(CO₂) distances are observed and diffraction experiments additionally reveal that secondary CO₂ adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contributemore » to adsorption behavior at ambient temperature. Density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO₂ angles and trends in relative geometric properties and heats of adsorption in the M₂(dobdc)–CO₂ adducts.« less

Authors:
 [1];  [2];  [3];  [3];  [3];  [1];  [3];  [1];  [1];  [4];  [4];  [5];  [4];  [1];  [3];  [1];  [3];  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. National Institute of Standards and Technology, Gaithersburg, MD (United States)
  3. Univ. of California, Berkeley, CA (United States)
  4. Australian Nuclear Science and Technology Organisation, Lucas Heights (Australia)
  5. Australia
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1162340
Resource Type:
Journal Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 5; Journal Issue: 12; Journal ID: ISSN 2041-6520: CSHCBM
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Queen, Wendy L., Hudson, Matthew R., Bloch, Eric D., Mason, Jarad A., Gonzalez, Miguel I., Lee, Jason S., Univ. of California, Berkeley, CA, Gygi, David, Howe, Joshua D., Univ. of California, Berkeley, CA, Lee, Kyuho, Univ. of California, Berkeley, CA, Darwish, Tamim A., James, Michael, Australian Synchrotron, Clayton, Peterson, Vanessa K., Teat, Simon J., Smit, Berend, Lawrence Berkeley National Lab., Ecole Polytechnique Federale de Lausanne, Neaton, Jeffrey B., Univ. of California, Berkeley, CA, Long, Jeffrey R., Lawrence Berkeley National Lab., Brown, Craig M., and Univ. of Delaware, Newark, DE. Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). United States: N. p., 2014. Web. doi:10.1039/C4SC02064B.
Queen, Wendy L., Hudson, Matthew R., Bloch, Eric D., Mason, Jarad A., Gonzalez, Miguel I., Lee, Jason S., Univ. of California, Berkeley, CA, Gygi, David, Howe, Joshua D., Univ. of California, Berkeley, CA, Lee, Kyuho, Univ. of California, Berkeley, CA, Darwish, Tamim A., James, Michael, Australian Synchrotron, Clayton, Peterson, Vanessa K., Teat, Simon J., Smit, Berend, Lawrence Berkeley National Lab., Ecole Polytechnique Federale de Lausanne, Neaton, Jeffrey B., Univ. of California, Berkeley, CA, Long, Jeffrey R., Lawrence Berkeley National Lab., Brown, Craig M., & Univ. of Delaware, Newark, DE. Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). United States. https://doi.org/10.1039/C4SC02064B
Queen, Wendy L., Hudson, Matthew R., Bloch, Eric D., Mason, Jarad A., Gonzalez, Miguel I., Lee, Jason S., Univ. of California, Berkeley, CA, Gygi, David, Howe, Joshua D., Univ. of California, Berkeley, CA, Lee, Kyuho, Univ. of California, Berkeley, CA, Darwish, Tamim A., James, Michael, Australian Synchrotron, Clayton, Peterson, Vanessa K., Teat, Simon J., Smit, Berend, Lawrence Berkeley National Lab., Ecole Polytechnique Federale de Lausanne, Neaton, Jeffrey B., Univ. of California, Berkeley, CA, Long, Jeffrey R., Lawrence Berkeley National Lab., Brown, Craig M., and Univ. of Delaware, Newark, DE. 2014. "Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)". United States. https://doi.org/10.1039/C4SC02064B.
@article{osti_1162340,
title = {Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)},
author = {Queen, Wendy L. and Hudson, Matthew R. and Bloch, Eric D. and Mason, Jarad A. and Gonzalez, Miguel I. and Lee, Jason S. and Univ. of California, Berkeley, CA and Gygi, David and Howe, Joshua D. and Univ. of California, Berkeley, CA and Lee, Kyuho and Univ. of California, Berkeley, CA and Darwish, Tamim A. and James, Michael and Australian Synchrotron, Clayton and Peterson, Vanessa K. and Teat, Simon J. and Smit, Berend and Lawrence Berkeley National Lab. and Ecole Polytechnique Federale de Lausanne and Neaton, Jeffrey B. and Univ. of California, Berkeley, CA and Long, Jeffrey R. and Lawrence Berkeley National Lab. and Brown, Craig M. and Univ. of Delaware, Newark, DE},
abstractNote = {Analysis of the CO₂ adsorption properties of a well-known series of metal–organic frameworks M₂(dobdc) (dobdc⁴⁻ = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO₂ adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO₂ within many of these materials while systematically varying both the amount of CO₂ and the temperature. Unlike previous studies, we show that CO₂ adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO₂ adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO₂. For the weaker CO₂ adsorbents, significant elongation of the metal–O(CO₂) distances are observed and diffraction experiments additionally reveal that secondary CO₂ adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contribute to adsorption behavior at ambient temperature. Density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO₂ angles and trends in relative geometric properties and heats of adsorption in the M₂(dobdc)–CO₂ adducts.},
doi = {10.1039/C4SC02064B},
url = {https://www.osti.gov/biblio/1162340}, journal = {Chemical Science},
issn = {2041-6520: CSHCBM},
number = 12,
volume = 5,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 2014},
month = {Wed Jan 01 00:00:00 EST 2014}
}

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