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

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. 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.

Authors:
 [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:
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)
OSTI Identifier:
1355145
Report Number(s):
NREL/JA-5900-68403
Journal ID: ISSN 0002-7863; TRN: US1702294
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 16; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; elemental halogens; metal-organic framework; MOF; storage; capture

Citation Formats

Tulchinsky, Yuri, Hendon, Christopher H., Lomachenko, Kirill A., Borfecchia, Elisa, Melot, Brent C., Hudson, Matthew R., Tarver, Jacob D., Korzyński, Maciej D., Stubbs, Amanda W., Kagan, Jacob J., Lamberti, Carlo, Brown, Craig M., and Dincă, Mircea. Reversible capture and release of Cl2 and Br2 with a redox-active metal–organic framework. United States: N. p., 2017. Web. doi:10.1021/jacs.7b02161.
Tulchinsky, Yuri, Hendon, Christopher H., Lomachenko, Kirill A., Borfecchia, Elisa, Melot, Brent C., Hudson, Matthew R., Tarver, Jacob D., Korzyński, Maciej D., Stubbs, Amanda W., Kagan, Jacob J., Lamberti, Carlo, Brown, Craig M., & Dincă, Mircea. Reversible capture and release of Cl2 and Br2 with a redox-active metal–organic framework. United States. doi:10.1021/jacs.7b02161.
Tulchinsky, Yuri, Hendon, Christopher H., Lomachenko, Kirill A., Borfecchia, Elisa, Melot, Brent C., Hudson, Matthew R., Tarver, Jacob D., Korzyński, Maciej D., Stubbs, Amanda W., Kagan, Jacob J., Lamberti, Carlo, Brown, Craig M., and Dincă, Mircea. Tue . "Reversible capture and release of Cl2 and Br2 with a redox-active metal–organic framework". United States. doi:10.1021/jacs.7b02161. https://www.osti.gov/servlets/purl/1355145.
@article{osti_1355145,
title = {Reversible capture and release of Cl2 and Br2 with a redox-active metal–organic framework},
author = {Tulchinsky, Yuri and Hendon, Christopher H. and Lomachenko, Kirill A. and Borfecchia, Elisa and Melot, Brent C. and Hudson, Matthew R. and Tarver, Jacob D. and Korzyński, Maciej D. and Stubbs, Amanda W. and Kagan, Jacob J. and Lamberti, Carlo and Brown, Craig M. and Dincă, Mircea},
abstractNote = {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.},
doi = {10.1021/jacs.7b02161},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 139,
place = {United States},
year = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}

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