1 research outputs found
Reversible Capture and Release of Cl<sub>2</sub> and Br<sub>2</sub> 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. These results highlight a material operating via redox mechanism
that may find utility in the storage and capture of other noxious
and corrosive gases