Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations1-4. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N2, through backbonding interactions5-7, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates8. 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 N2 capacities and selectivities for the removal of N2 from mixtures with CH4, 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.
Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites / D.E. Jaramillo, D.A. Reed, H.Z.H. Jiang, J. Oktawiec, M.W. Mara, A.C. Forse, D.J. Lussier, R.A. Murphy, M. Cunningham, V. COLOMBO, D.K. Shuh, J.A. Reimer, J.R. Long. - In: NATURE MATERIALS. - ISSN 1476-1122. - (2020 Feb 03). [Epub ahead of print]
|Titolo:||Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
Settore CHIM/02 - Chimica Fisica
|Data di pubblicazione:||3-feb-2020|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1038/s41563-019-0597-8|
|Appare nelle tipologie:||01 - Articolo su periodico|