Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66
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...
| Main Authors: | , , , , |
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| Format: | Journal Article |
| Published: |
American Chemical Society
2016
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| Online Access: | http://hdl.handle.net/20.500.11937/12322 |
| _version_ | 1848748044293505024 |
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| author | Bristow, J. Svane, K. Tiana, D. Skelton, J. Gale, Julian |
| author_facet | Bristow, J. Svane, K. Tiana, D. Skelton, J. Gale, Julian |
| author_sort | Bristow, J. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T06:58:47Z |
| format | Journal Article |
| id | curtin-20.500.11937-12322 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T06:58:47Z |
| publishDate | 2016 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-123222017-09-13T14:59:51Z Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 Bristow, J. Svane, K. Tiana, D. Skelton, J. Gale, Julian 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. 2016 Journal Article http://hdl.handle.net/20.500.11937/12322 10.1021/acs.jpcc.6b01659 American Chemical Society unknown |
| spellingShingle | Bristow, J. Svane, K. Tiana, D. Skelton, J. Gale, Julian Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title | Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title_full | Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title_fullStr | Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title_full_unstemmed | Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title_short | Free Energy of Ligand Removal in the Metal–Organic Framework UiO-66 |
| title_sort | free energy of ligand removal in the metal–organic framework uio-66 |
| url | http://hdl.handle.net/20.500.11937/12322 |