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Title: Reversible and Selective O 2 Chemisorption in a Porous Metal-Organic Host Material

Abstract

The metal-organic host material [{Co III 2(bpbp)(O 2)} 2bdc](PF 6) 4 (1 ∙ 2O 2; bpbp- = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc 2- = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{Co II 2(bpbp)} 2bdc](PF 6) 4 (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1 ∙ 2O 2, achieved through desorption of included water guests from the as-synthesized phase 1 ∙ 2O 2 ∙ 3H 2O, 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 ∙ 2O 2 indicate the potential suitability of this material for air separation, with a O 2/N 2 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 complexmore » when it is incorporated in a porous solid.« less

Authors:
; ; ; ;  [1];  [2]
  1. Sydney
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1027135
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 133; Journal Issue: 28; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION ISOTHERMS; AFFINITY; AIR; CAPACITY; CHEMISORPTION; DESORPTION; GASES; MONOCRYSTALS; OXYGEN; WATER; X-RAY DIFFRACTION

Citation Formats

Southon, Peter D, Price, David J, Nielsen, Pia K, McKenzie, Christine J, Kepert, Cameron J, and USD-Netherlands). Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material. United States: N. p., 2011. Web. doi:10.1021/ja202228v.
Southon, Peter D, Price, David J, Nielsen, Pia K, McKenzie, Christine J, Kepert, Cameron J, & USD-Netherlands). Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material. United States. doi:10.1021/ja202228v.
Southon, Peter D, Price, David J, Nielsen, Pia K, McKenzie, Christine J, Kepert, Cameron J, and USD-Netherlands). Thu . "Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material". United States. doi:10.1021/ja202228v.
@article{osti_1027135,
title = {Reversible and Selective O2 Chemisorption in a Porous Metal-Organic Host Material},
author = {Southon, Peter D and Price, David J and Nielsen, Pia K and McKenzie, Christine J and Kepert, Cameron J and USD-Netherlands)},
abstractNote = {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.},
doi = {10.1021/ja202228v},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 28,
volume = 133,
place = {United States},
year = {2011},
month = {11}
}