1 iNano-School, Science and Technology, Aarhus University2 Department of Physics and Astronomy, Science and Technology, Aarhus University3 Interdisciplinary Nanoscience Center - INANO-Fysik, Ny Munkegade, Interdisciplinary Nanoscience Center, Science and Technology, Aarhus University4 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology5 Interdisciplinary Nanoscience Center - INANO-Fysik, Ny Munkegade, Interdisciplinary Nanoscience Center, Science and Technology, Aarhus University
Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory calculations to predict the structure of Pd clusters in UiO-66. The cluster sizes examined are far larger than those in any previous modeling studies of metal clusters in MOFs and allow us to test the hypothesis that the physically separated cavities in UiO-66 could stabilize isolated Pd clusters. Our calculations show that Pd clusters in UiO-66 are, at best, metastable and will aggregate into connected pore filling structures at equilibrium.
Journal of Physical Chemistry Letters, 2012, Vol 3