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

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dc.contributor.authorQueen, WLen_AU
dc.contributor.authorHudson, MRen_AU
dc.contributor.authorBloch, EDen_AU
dc.contributor.authorMason, JAen_AU
dc.contributor.authorGonzalez, MIen_AU
dc.contributor.authorLee, JSen_AU
dc.contributor.authorGygi, Den_AU
dc.contributor.authorHowe, JDen_AU
dc.contributor.authorLee, Ken_AU
dc.contributor.authorDarwish, TAen_AU
dc.contributor.authorJames, Men_AU
dc.contributor.authorPeterson, VKen_AU
dc.contributor.authorTeat, SJen_AU
dc.contributor.authorSmit, Ben_AU
dc.contributor.authorNeaton, JBen_AU
dc.contributor.authorLong, JRen_AU
dc.contributor.authorBrown, CMen_AU
dc.date.accessioned2016-10-19T00:43:15Zen_AU
dc.date.available2016-10-19T00:43:15Zen_AU
dc.date.issued2014-08-28en_AU
dc.date.statistics2016-10-10en_AU
dc.description.abstractAnalysis 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. © 2014, The Royal Society of Chemistry.en_AU
dc.identifier.citationQueen, W. L., Hudson, M. R., Bloch, E. D., Mason, J. A., Gonzalez, M. I., Lee, J. S., Gygi, D., Howe, J. D., Lee, K., Darwish, T. A., James, M., Peterson, V. K., Treat, S. J., Smit, B., Neaton, J. B., Long, J. R., & Brown, C. M. (2014). Comprehensive study of carbon dioxide adsorption in the metal-organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn). Chemical Science, 5(12), 4569-4581. doi:10.1039/C4SC02064Ben_AU
dc.identifier.govdoc7363en_AU
dc.identifier.issn2041-6539en_AU
dc.identifier.issue12en_AU
dc.identifier.journaltitleChemical Scienceen_AU
dc.identifier.pagination4569-4581en_AU
dc.identifier.urihttp://dx.doi.org/10.1039/c4sc02064ben_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/7800en_AU
dc.identifier.volume5en_AU
dc.language.isoenen_AU
dc.publisherRoyal Society of Chemistryen_AU
dc.subjectFossil fuelsen_AU
dc.subjectNeutronsen_AU
dc.subjectAdsorptionen_AU
dc.subjectMetalsen_AU
dc.subjectCarbon dioxideen_AU
dc.subjectSeparation processesen_AU
dc.titleComprehensive study of carbon dioxide adsorption in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)en_AU
dc.typeJournal Articleen_AU
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