Design of a metal-organic framework with enhanced back bonding for the separation of N2 and CH4

ORAL

Abstract

Removing dinitrogen, an omnipresent but noncombustible contaminant, from natural gas or other methane-rich gases is an extraordinarily difficult separation based on physical properties alone, as both gases lack a permanent dipole and have similar polarizabilities, boiling points, and kinetic diameters. In this work, by using dispersion-corrected density functionals and wavefunction approaches, we predict a new metal-organic framework (MOF) of potential utility for the highly selective and efficient separation of dinitrogen from methane, a particularly challenging separation of critical value for utilizing natural gas. Selective back bonding interactions from the vanadium(II) cation centers in V-MOF-74 to the unoccupied $\pi$* orbitals of N2 can be used to separate N2/CH4 mixtures. We compare our calculations with the experimentally characterized Fe-MOF-74.

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Authors

  • Kyuho Lee

    • Dept. of Chemical and Biomolecular Engineering, University of California, Berkeley; The Molecular Foundry, LBNL
    • Molecular Foundry, Berkeley Lab

  • William Isley

    • Department of Chemistry, University of Minnesota

  • Allison Dzubak

    • Department of Chemistry, University of Minnesota

  • Pragya Verma

    • Department of Chemistry, University of Minnesota

  • Samuel Stoneburner

    • Department of Chemistry, University of Minnesota

  • Li-Chiang Lin

    • Department of Chemical and Biomolecular Engineering, UC Berkeley

  • Joshua Howe

    • Department of Chemical and Biomolecular Engineering, UC Berkeley

  • Eric Bloch

    • Department of Chemistry, UC Berkeley

  • Douglas Reed

    • Department of Chemistry, UC Berkeley

  • Matthew Hudson

    • Center for Neutron Research, NIST

  • Craig Brown

    • Center for Neutron Research, NIST

  • Jeffrey Long

    • Department of Chemistry, UC Berkeley

  • Jeffrey B. Neaton

    • Department of Physics, UC Berkeley

  • Berend Smit

    • Department of Chemical and Biomolecular Engineering, UC Berkeley

  • Christopher J. Cramer

    • Department of Chemistry, University of Minnesota

  • Donald G. Truhlar

    • Department of Chemistry, University of Minnesota

  • Laura Gagliardi

    • Department of Chemistry, University of Minnesota