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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Abstract

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
Volume120
Issue number17
Early online date12 Apr 2016
DOIs
Publication statusPublished - 5 May 2016

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Free energy
Metals
free energy
Ligands
Defects
ligands
defects
metals
dynamic structural analysis
Structural dynamics
energy of formation
Benzene
acetic acid
Acetic acid
Acetic Acid
Materials properties
benzene
energy

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Bristow, J., Svane, K., Tiana, D., Skelton, J., Gale, J. D., & Walsh, A. (2016). Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66. Journal of Physical Chemistry C, 120(17), 9276-9281. https://doi.org/10.1021/acs.jpcc.6b01659

Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66. / Bristow, Jessica; Svane, Katrine; Tiana, Davide; Skelton, Jonathan; Gale, Julian D.; Walsh, Aron.

In: Journal of Physical Chemistry C, Vol. 120, No. 17, 05.05.2016, p. 9276-9281.

Research output: Contribution to journalArticle

Bristow, J, Svane, K, Tiana, D, Skelton, J, Gale, JD & Walsh, A 2016, 'Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66', Journal of Physical Chemistry C, vol. 120, no. 17, pp. 9276-9281. https://doi.org/10.1021/acs.jpcc.6b01659
Bristow J, Svane K, Tiana D, Skelton J, Gale JD, Walsh A. Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66. Journal of Physical Chemistry C. 2016 May 5;120(17):9276-9281. https://doi.org/10.1021/acs.jpcc.6b01659
Bristow, Jessica ; Svane, Katrine ; Tiana, Davide ; Skelton, Jonathan ; Gale, Julian D. ; Walsh, Aron. / Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66. In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 17. pp. 9276-9281.
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