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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b02161· OSTI ID:1355145
 [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)
+ Show Author Affiliations

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; TRN: US1702294
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 16; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 77 works
Citation information provided by
Web of Science

References (24)

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Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2 journal June 2010
Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks journal May 2016
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High volumetric uptake of ammonia using Cu-MOF-74/Cu-CPO-27 journal January 2016
High and Reversible Ammonia Uptake in Mesoporous Azolate Metal–Organic Frameworks with Open Mn, Co, and Ni Sites journal July 2016
Stereoselective Halogenation of Integral Unsaturated C-C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs journal February 2016
Ti 3+ -, V 2+/3+ -, Cr 2+/3+ -, Mn 2+ -, and Fe 2+ -Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5 journal August 2013
Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites journal May 2014
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Synthesis, characterization and CO2 uptake of a chiral Co(ii) metal–organic framework containing a thiazolidine-based spacer journal January 2012
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Application of Large Pore MCM-41 Molecular Sieves To Improve Pore Size Analysis Using Nitrogen Adsorption Measurements journal November 1997
Removal of chlorine gas by an amine functionalized metal–organic framework via electrophilic aromatic substitution journal January 2015
3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation journal March 2015
Turning on the flexibility of isoreticular porous coordination frameworks for drastically tunable framework breathing and thermal expansion journal January 2013
Heterogeneous Catalytic Oxidation by MFU-1: A Cobalt(II)-Containing Metal-Organic Framework journal September 2009
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Photochemical and thermal cobalt-carbon bond cleavage in alkylcobalamins and related organometallic compounds. Comparative study journal November 1968

Cited By (14)

Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal January 2019
Sodium-coupled electron transfer reactivity of metal–organic frameworks containing titanium clusters: the importance of cations in redox chemistry journal January 2019
Binding of halogens by a Cr 8 metallacrown journal January 2018
A Systematic Study of Isomorphically Substituted H-MAlPO-5 Materials for the Methanol-to-Hydrocarbons Reaction journal December 2017
Metallopolymers for advanced sustainable applications journal January 2019
Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles journal January 2020
Adsorption and sequential thermal release of F 2 , Cl 2 , and Br 2 molecules by a porous organic cage material (CC3‐R): Molecular dynamics and grand‐canonical Monte Carlo simulations journal December 2019
Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions journal October 2017
Spectroscopic characterization of metal ligation in trinuclear iron-μ 3 -oxo-based complexes and metal-organic frameworks journal May 2019
Construction of Porous Aromatic Frameworks with Exceptional Porosity via Building Unit Engineering journal September 2018
Redox-active metal–organic frameworks for energy conversion and storage journal January 2019
Neutron diffraction structural study of CO 2 binding in mixed-metal CPM-200 metal–organic frameworks journal January 2020
Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture journal September 2019
Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions journal October 2017

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Related Subjects

36 MATERIALS SCIENCE
elemental halogens
metal-organic framework
MOF
storage
capture