title: Reversible Capture and Release of Cl2and Br2with 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. 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.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Yuri
authors.initials: Y
authors.lastname: Tulchinsky
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Christopher H
authors.identifier: 0000-0002-7132-768X
authors.initials: CH
authors.lastname: Hendon
authors.affiliation: European Synchrotron Radiation Facility , 71 Avenue des Martyrs, CS 40220, 38043 Grenoble Cedex 9, France.|IRC "Smart Materials", Southern Federal University , Zorge Street 5, 344090 Rostov-on-Don, Russia.
authors.forename: Kirill A
authors.initials: KA
authors.lastname: Lomachenko
authors.affiliation: Department of Chemistry, NIS, CrisDi, and INSTM Centre of Reference, University of Turin , Via Quarello 15, I-10135 Torino, Italy.
authors.forename: Elisa
authors.initials: E
authors.lastname: Borfecchia
authors.affiliation: Department of Chemistry, University of Southern California , 3620 McClintock Avenue, Los Angeles, California 90089-1062, United States.
authors.forename: Brent C
authors.initials: BC
authors.lastname: Melot
authors.affiliation: Center for Neutron Research, National Institute of Standards and Technology , Gaithersburg, Maryland 20899, United States.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Hudson
authors.affiliation: Center for Neutron Research, National Institute of Standards and Technology , Gaithersburg, Maryland 20899, United States.|National Renewable Energy Laboratory , 15013 Denver West Parkway, Golden, Colorado 80401, United States.
authors.forename: Jacob D
authors.initials: JD
authors.lastname: Tarver
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Maciej D
authors.initials: MD
authors.lastname: Korzyński
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Amanda W
authors.initials: AW
authors.lastname: Stubbs
authors.affiliation: Department of Mathematics, Weizmann Institute of Science , 234 Herzl Street, Rehovot 7610001, Israel.
authors.forename: Jacob J
authors.initials: JJ
authors.lastname: Kagan
authors.affiliation: IRC "Smart Materials", Southern Federal University , Zorge Street 5, 344090 Rostov-on-Don, Russia.|Department of Chemistry, NIS, CrisDi, and INSTM Centre of Reference, University of Turin , Via Quarello 15, I-10135 Torino, Italy.
authors.forename: Carlo
authors.identifier: 0000-0001-8004-2312
authors.initials: C
authors.lastname: Lamberti
authors.affiliation: Center for Neutron Research, National Institute of Standards and Technology , Gaithersburg, Maryland 20899, United States.
authors.forename: Craig M
authors.initials: CM
authors.lastname: Brown
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Mircea
authors.identifier: 0000-0002-1262-1264
authors.initials: M
authors.lastname: Dincă