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Cited by 531

The DOI matches its Crossref record; 71 of the 71 references it cites were found in a registry or an index.

Selective Binding of O2 over N2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites

Open access
Bloch, Eric D., Murray, Leslie J., Queen, Wendy L., Chavan, Sachin, Maximoff, Sergey N., Bigi, Julian P., Krishna, Rajamani, Peterson, Vanessa K., Grandjean, Fernande, Long, Gary J., Smit, Berend, Bordiga, Silvia, Brown, Craig M., Long, Jeffrey R.·2011·Journal of the American Chemical Society
DOI 10.1021/ja205976v
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Abstract

The air-free reaction between FeCl(2) and H(4)dobdc (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe(2)(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 m(2)/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe(II) centers. Gas adsorption isotherms at 298 K indicate that Fe(2)(dobdc) binds O(2) preferentially over N(2), with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O(2) molecule per two iron centers. Remarkably, at 211 K, O(2) uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O(2) molecule per iron center. Mössbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O(2) at low temperature and complete charge transfer to form iron(III) and O(2)(2-) at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O(2) bound to iron in a symmetric side-on mode with d(O-O) = 1.25(1) Å at low temperature and in a slipped side-on mode with d(O-O) = 1.6(1) Å when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe(2)(dobdc) to be a promising material for the separation of O(2) from air at temperatures well above those currently employed in industrial settings.

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Metadata

Authors
Bloch, 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.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2011-08-26
Volume
133
Issue
37
Pages
14814-14822
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja205976v
OpenAlex
W2104595982
Cited by
531
References
71
FWCI
20.06
Type
journal article
Language
en
Open access
green

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