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Title: Reversible capture and release of Cl 2 and Br 2 with a redox-active metal–organic framework

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. Finally, these results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.
 [1] ; ORCiD logo [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [6] ;  [1] ;  [1] ;  [7] ; ORCiD logo [8] ;  [5] ; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. European Synchrotron Radiation Facility, Grenoble Cedex (France); Southern Federal Univ., Rostov-on-Don (Russia)
  3. Univ. of Turin, Torino (Italy)
  4. Univ. of Southern California, Los Angeles, CA (United States)
  5. National Institute of Standards and Technology, Gaithersburg, MD (United States)
  6. National Institute of Standards and Technology, Gaithersburg, MD (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  7. Weizmann Institute of Science, Rehovot (Israel)
  8. Univ. of Turin, Torino (Italy); Southern Federal Univ., Rostov-on-Don (Russia)
Publication Date:
Report Number(s):
Journal ID: ISSN 0002-7863; TRN: US1702294
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 16; Journal ID: ISSN 0002-7863
American Chemical Society (ACS)
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F)
Country of Publication:
United States
36 MATERIALS SCIENCE; elemental halogens; metal-organic framework; MOF; storage; capture
OSTI Identifier: