Selective binding of O(2) over N(2) in a redox-active metal-organic framework with open iron(II) coordination sites

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dc.contributor.authorBloch, EDen_AU
dc.contributor.authorMurray, LJen_AU
dc.contributor.authorQueen, WLen_AU
dc.contributor.authorChavan, Sen_AU
dc.contributor.authorMaximoff, SNen_AU
dc.contributor.authorBigi, JPen_AU
dc.contributor.authorKrishna, Ren_AU
dc.contributor.authorPeterson, VKen_AU
dc.contributor.authorGrandjean, Fen_AU
dc.contributor.authorLong, GJen_AU
dc.contributor.authorSmit, Ben_AU
dc.contributor.authorBordiga, Sen_AU
dc.contributor.authorBrown, CMen_AU
dc.contributor.authorLong, JRen_AU
dc.date.accessioned2011-11-22T02:53:00Zen_AU
dc.date.available2011-11-22T02:53:00Zen_AU
dc.date.issued2011-09-21en_AU
dc.date.statistics2011-11-18en_AU
dc.description.abstractThe air-free reaction between FeCl2 and H4dobdc (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe2(dobdc)·4DMF, a metal–organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer–Emmett–Teller (BET) surface area of 1360 m2/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated FeII centers. Gas adsorption isotherms at 298 K indicate that Fe2(dobdc) binds O2 preferentially over N2, with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O2 molecule per two iron centers. Remarkably, at 211 K, O2 uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O2 molecule per iron center. Mössbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O2 at low temperature and complete charge transfer to form iron(III) and O22– at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O2 bound to iron in a symmetric side-on mode with dO–O = 1.25(1) Ã… at low temperature and in a slipped side-on mode with dO–O = 1.6(1) Ã… when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe2(dobdc) to be a promising material for the separation of O2 from air at temperatures well above those currently employed in industrial settings. © 2011, American Chemical Societyen_AU
dc.identifier.citationBloch, E. D., Murray, L .J., Queen, W. L., Chavan, S., Maximoff, S. N., Bigi, J. P., Krishna, R., Peterson, V. K., Grandjean, F., Long, G. J., Smit, B., Bordiga, S., Brown, C. M., & Long, J. R. (2011). Selective binding of O(2) over N(2) in a redox-active metal-organic framework with open iron(II) coordination sites. Journal of the American Chemical Society, 133(37), 14814-14822. doi:10.1021/ja205976ven_AU
dc.identifier.govdoc3784en_AU
dc.identifier.issn0002-7863en_AU
dc.identifier.issue37en_AU
dc.identifier.journaltitleJournal of the American Chemical Societyen_AU
dc.identifier.pagination14814-14822en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/ja205976ven_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/3878en_AU
dc.identifier.volume133en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectHydrogenen_AU
dc.subjectCrystal structureen_AU
dc.subjectAdductsen_AU
dc.subjectAdsorptionen_AU
dc.subjectNeutron diffractionen_AU
dc.subjectIronen_AU
dc.titleSelective binding of O(2) over N(2) in a redox-active metal-organic framework with open iron(II) coordination sitesen_AU
dc.typeJournal Articleen_AU
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