Free energy of ligand removal in the metal-organic framework UiO-66

Jessica K. Bristow, Katrine L. Svane, Davide Tiana, Jonathan M. Skelton, Julian D. Gale, Aron Walsh

    Research output: Contribution to journalArticlepeer-review

    Abstract

    We report an investigation of the "missing-linker phenomenon" in the Zr-based metal-organic framework UiO-66 using atomistic force field and quantum chemical methods. For a vacant benzene dicarboxylate ligand, the lowest energy charge-capping mechanism involves acetic acid or Cl-/H2O. The calculated defect free energy of formation is remarkably low, consistent with the high defect concentrations reported experimentally. A dynamic structural instability is identified for certain higher defect concentrations. In addition to the changes in material properties upon defect formation, we assess the formation of molecular aggregates, which provide an additional driving force for ligand loss. These results are expected to be of relevance to a wide range of metal-organic frameworks.

    Original languageEnglish
    Pages (from-to)9276-9281
    Number of pages6
    JournalJournal of Physical Chemistry C
    Volume120
    Issue number17
    DOIs
    Publication statusPublished - 12 Apr 2016

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