Ab Initio Molecular Dynamic Simulations on Pd Clusters Confined in UiO-66-NH2

The thermodynamically stable metal organic framework UiO-66-NH 2 has experimentally been demonstrated as an ideal platform to isolate metal clusters within its nanocages; however, the electronic structures and the dynamics of the encapsulated metal clusters are still unclear. Ab initio molecular dynamics simulations combined with density functional theory-based methods were employed to search the stable structures of Pd n @UiO-66-NH 2 composites, and their electronic properties were analyzed in detail. We found that the thermodynamics of the composites are highly correlated with charge transfer between the Pd n cluster and the UiO-66-NH 2 framework, as well as the deformation energy of the framework. In addition, both ab initio molecular dynamics simulations and density functional theory calculations show that the small Pd clusters can easily diffuse into the tetrahedral cage of UiO-66-NH 2 from the octahedral cage through the window connecting these two types of cages, with a small energy barrier.