Free Energy of Ligand Removal in the Metal-Organic Framework UiO-66
File(s)
Author(s)
Type
Journal Article
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.
Date Issued
2016-05-05
Date Acceptance
2016-04-12
Citation
Journal of Physical Chemistry C, 2016, 120 (17), pp.9276-9281
ISSN
1932-7455
Publisher
American Chemical Society
Start Page
9276
End Page
9281
Journal / Book Title
Journal of Physical Chemistry C
Volume
120
Issue
17
Copyright Statement
This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
License URL
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Chemistry
Science & Technology - Other Topics
Materials Science
DENSITY FUNCTIONALS
MOFS
PROGRAM
ADSORPTION
DEFECTS
GULP
Publication Status
Published