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

David E. Jaramillo, Douglas A. Reed, Henry Z.H. Jiang, Julia Oktawiec, Michael W. Mara, Alexander C. Forse, Daniel J. Lussier, Ryan A. Murphy, Marc Cunningham, Valentina Colombo, David K. Shuh, Jeffrey A. Reimer, Jeffrey R. Long*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)517-521
Number of pages5
JournalNature materials
Issue number5
StatePublished - May 1 2020
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering

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