Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations . Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N , through...

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Bibliographic Details
Published in:Nature materials 2020-05, Vol.19 (5), p.517-521
Main Authors: Jaramillo, David E, Reed, Douglas A, Jiang, Henry Z H, Oktawiec, Julia, Mara, Michael W, Forse, Alexander C, Lussier, Daniel J, Murphy, Ryan A, Cunningham, Marc, Colombo, Valentina, Shuh, David K, Reimer, Jeffrey A, Long, Jeffrey R
Format: Article
Language:English
Subjects:
Acidity
Adsorbents
Adsorption
Electron density
Exposure
High temperature
Metal-organic frameworks
Metals
Methane
Paraffins
Porous materials
Selectivity
Transition metals
Vanadium
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Summary:Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations . Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N , through backbonding interactions , and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates . Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N capacities and selectivities for the removal of N from mixtures with CH , while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents.
ISSN:1476-1122
1476-4660
DOI:10.1038/s41563-019-0597-8