Reversible capture and release of Cl₂ and Br₂ with a redox-active metal–organic framework

Journal Article · Tue Mar 28 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.7b02161 · OSTI ID:1355145

Tulchinsky, Yuri ^[1]; Hendon, Christopher H.  ^[1]; Lomachenko, Kirill A. ^[2]; Borfecchia, Elisa ^[3]; Melot, Brent C. ^[4]; Hudson, Matthew R. ^[5]; Tarver, Jacob D. ^[6]; Korzyński, Maciej D. ^[1]; Stubbs, Amanda W. ^[1]; Kagan, Jacob J. ^[7]; Lamberti, Carlo  ^[8]; Brown, Craig M. ^[5]; Dincă, Mircea  ^[1]

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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)

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.

• Research Organization: National Renewable Energy Lab. (NREL), Golden, CO (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F)
• Grant/Contract Number: AC36-08GO28308
• OSTI ID: 1355145
• Report Number(s): NREL/JA--5900-68403
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 16 Vol. 139; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)Copyright Statement
• Country of Publication: United States
• Language: English