Vacancy lattice sites in the metal-organic framework UiO-66 are known to have a profound effect on the material properties. Here we use density functional theory to compare the energies of defect arrangements containing missing linkers and missing metal clusters for different choices of charge compensation. Our results show that the preference for missing metal clusters or missing linker defects depends on the charge compensation as well as the overall concentration of defects in the crystal. Both regimes can be experimentally accessible depending on the synthesis conditions. We investigate the electronic structure of the different types of defects, showing that, despite some changes in the localisation of the frontier orbitals, the electronic energy levels are only weakly affected by the presence of point defects.
Bibliographical noteFunding Information:
K. L. S. is funded by ERC programme grant no. 277757 and J. K. B. is funded by the EPSRC (grant no. EP/G03768X/1). J. D. G. thanks the Australian Research Council for funding through the Discovery Programme. The authors acknowledge computing support from the UK national supercomputing service (Archer), via membership of the UK Materials Chemistry Consortium which is funded by EPSRC (EP/L000202), and from the University of Bath computing services (Balena).
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)