Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework
Name
jacs.7b02161.pdf
Size
2.68 MB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Lomachenko, Kirill A.
Borfecchia, Elisa
Melot, Brent C.
Hudson, Matthew R.
Tarver, Jacob D.
Kagan, Jacob J.
Lamberti, Carlo
Brown, Craig M.
Tulchinsky, Yuri
Hendon, Christopher H
Date Issued
January 23, 2018
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Tulchinsky, Yuri et al. “Reversible Capture and Release of Cl₂ and Br₂ with a Redox-Active Metal–Organic Framework.” Journal of the American Chemical Society 139, 16 (April 2017): 5992–5997 © 2017 American Chemical Society
Version
Final published version
Abstract
Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/JACS.7B02161
