Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material
- Sydney
The metal-organic host material [{CoIII2(bpbp)(O2)}2bdc](PF6)4 (1 ∙ 2O2; bpbp- = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc2- = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{CoII2(bpbp)}2bdc](PF6)4 (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1 ∙ 2O2, achieved through desorption of included water guests from the as-synthesized phase 1 ∙ 2O2 ∙ 3H2O, consists of an ionic lattice containing discrete tetranuclear complexes, between which lie void regions that allow the migration of dioxygen and other guests. Powder X-ray diffraction analyses indicate that the host material retains crystallinity through the dioxygen desorption/chemisorption processes. Dioxygen chemisorption measurements on 1 show near-stoichiometric uptake of dioxygen at 5 mbar and 25 °C, and this capacity is largely retained at temperatures above 100 °C. Gas adsorption isotherms of major atmospheric gases on both 1 and 1 ∙ 2O2 indicate the potential suitability of this material for air separation, with a O2/N2 selectivity factor of 38 at 1 atm. Comparison of oxygen binding in solution and in the solid state indicates a dramatic increase in binding affinity to the complex when it is incorporated in a porous solid.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Organization:
- FOREIGN
- OSTI ID:
- 1027135
- Journal Information:
- Journal of the American Chemical Society, Vol. 133, Issue 28; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- ENGLISH
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