Svane Katrine L, Bristow Jessica K, Gale Julian D, Walsh Aron
Department of Chemistry , University of Bath , Bath , UK . Email:
Curtin Institute for Computation , Department of Chemistry , Curtin University , PO Box U1987 , Perth , WA 6845 , Australia.
J Mater Chem A Mater. 2018 May 14;6(18):8507-8513. doi: 10.1039/c7ta11155j. Epub 2018 Apr 24.
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.
金属有机框架UiO-66中的空位晶格位点对材料性能有深远影响。在此，我们使用密度泛函理论来比较不同电荷补偿选择下包含缺失连接体和缺失金属簇的缺陷排列的能量。我们的结果表明，对缺失金属簇或缺失连接体缺陷的偏好取决于电荷补偿以及晶体中缺陷的总体浓度。根据合成条件，这两种情况在实验上都是可实现的。我们研究了不同类型缺陷的电子结构，结果表明，尽管前沿轨道的局域化有一些变化，但电子能级仅受到点缺陷存在的微弱影响。
