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

45 Scopus citations


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
Issue number17
StatePublished - 5 May 2016

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© 2016 American Chemical Society.


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