Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66

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

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30 Citations (SciVal)
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We report an investigation of the `missing-linker phenomenon' in the Zr-based metal-organic framework UiO-66 using atomistic forcefield 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
JournalJournal of Physical Chemistry C
Issue number17
Early online date12 Apr 2016
Publication statusPublished - 5 May 2016


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