Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); University of Minnesota Nanoporous Materials Genome Center
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Australian Nuclear Science and Technology Organisation, Lucas Heights (Australia)
Australian Nuclear Science and Technology Organisation, Lucas Heights (Australia); Australian Synchrotron, Clayton (Australia)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
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. In conclusion, 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.
Queen, Wendy L., et al. "Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M<sub>2</sub>(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)." Chemical Science, vol. 5, no. 12, Aug. 2014. https://doi.org/10.1039/C4SC02064B
Queen, Wendy L., Hudson, Matthew R., Bloch, Eric D., Mason, Jarad A., Gonzalez, Miguel I., Lee, Jason S., Gygi, David, Howe, Joshua D., Lee, Kyuho, Darwish, Tamim A., James, Michael, Peterson, Vanessa K., Teat, Simon J., Smit, Berend, Neaton, Jeffrey B., Long, Jeffrey R., & Brown, Craig M. (2014). Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M<sub>2</sub>(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). Chemical Science, 5(12). https://doi.org/10.1039/C4SC02064B
Queen, Wendy L., Hudson, Matthew R., Bloch, Eric D., et al., "Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M<sub>2</sub>(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)," Chemical Science 5, no. 12 (2014), https://doi.org/10.1039/C4SC02064B
@article{osti_1459348,
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 Gygi, David and Howe, Joshua D. and Lee, Kyuho and Darwish, Tamim A. and others},
title = {Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M<sub>2</sub>(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)},
annote = {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. In conclusion, 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/1459348},
journal = {Chemical Science},
issn = {ISSN CSHCBM},
number = {12},
volume = {5},
place = {United States},
publisher = {Royal Society of Chemistry},
year = {2014},
month = {08}}
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 588, Issue 3https://doi.org/10.1016/j.nima.2008.02.006
Smith, Rebecca; Vitórica-Yrezábal, Iñigo J.; Hill, Adrian
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, Issue 2084https://doi.org/10.1098/rsta.2016.0031
