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Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal-organic framework
- Source :
- Nature communications, vol 11, iss 1, Nature Communications, Nature Communications, Vol 11, Iss 1, Pp 1-11 (2020)
- Publication Year :
- 2020
- Publisher :
- eScholarship, University of California, 2020.
-
Abstract
- The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co2(OH)2(bbta) (H2bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) leads to strong and reversible adsorption of O2. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O2 adsorption. Notably, O2-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal–organic frameworks for adsorption-based applications.<br />Oxygen capture is attractive for catalysis, sensing, and separations, but engineering stable and selective adsorbents is challenging. Here the authors combine metal-based electron transfer with secondary coordination sphere effects in a metal-organic framework, leading to strong and reversible O2 adsorption that also exhibits negative cooperativity.
- Subjects :
- Coordination sphere
Science
General Physics and Astronomy
chemistry.chemical_element
02 engineering and technology
010402 general chemistry
Photochemistry
01 natural sciences
General Biochemistry, Genetics and Molecular Biology
Article
Metal
Electron transfer
Adsorption
Electronic effect
lcsh:Science
Multidisciplinary
Hydrogen bond
General Chemistry
Metal-organic frameworks
021001 nanoscience & nanotechnology
0104 chemical sciences
chemistry
visual_art
visual_art.visual_art_medium
Metal-organic framework
lcsh:Q
Materials chemistry
0210 nano-technology
Cobalt
Inorganic chemistry
Subjects
Details
- Database :
- OpenAIRE
- Journal :
- Nature communications, vol 11, iss 1, Nature Communications, Nature Communications, Vol 11, Iss 1, Pp 1-11 (2020)
- Accession number :
- edsair.doi.dedup.....126d076f6a9fdcb95b059afc2bcccf8e