Reversible Capture and Release of Cl2 and Br2 with a Redox-Active Metal–Organic Framework
| Autor: | Jacob Tarver, Amanda W. Stubbs, Yuri Tulchinsky, Matthew R. Hudson, Jacob J. Kagan, Mircea Dincă, Elisa Borfecchia, Brent C. Melot, Maciej D. Korzyński, Craig M. Brown, Carlo Lamberti, Christopher H. Hendon, Kirill A. Lomachenko |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
inorganic chemicals
Inorganic chemistry chemistry.chemical_element 02 engineering and technology Thermal treatment 010402 general chemistry 01 natural sciences Biochemistry Catalysis Chemical storage Crystallinity Colloid and Surface Chemistry Chlorine Coordinatively unsaturated Elemental halogens Bond cleavage X-ray absorption spectroscopy Bromine In situ characterization General Chemistry 021001 nanoscience & nanotechnology Non-volatile compounds 0104 chemical sciences X-ray Absorption Spectroscopy Chemical storage Coordinatively unsaturated Elemental halogens Homolytic cleavage Metal organic framework Non-volatile compounds Oxidation/reduction Redox-active metals X-ray Absorption Spectroscopy In situ characterization Metal organic framework Redox-active metals chemistry Halogen Oxidation/reduction Metal-organic framework Homolytic cleavage 0210 nano-technology |
| Zdroj: | Journal of the American Chemical Society. 139:5992-5997 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.7b02161 |
| Popis: | 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 oxid... |
| Databáze: | OpenAIRE |
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