Abstract
The effect of cluster size, oxidation state, and the support upon the structures and energetics of subnanometer palladium nanoparticles is investigated within a density functional framework. Gas phase global minima of Pd and Pd along with their suboxide counterparts are determined using a genetic algorithm and deposited upon MgO (001) and a high-index alumina surface. It is observed that there is an oxidation-dependent transition in the smaller clusters from three-dimensional to two-dimensional structures both in the gas phase and when supported by a surface. MgO strongly promotes a change from tetrahedral- and icosahedral-based structures toward cubic forms, while alumina induces significant distortion of the cluster and the breaking of Pd-Pd bonds. Increased oxygenation contributes cooperatively to these effects, causing disruption of the Pd-Pd bond network, favoring the incorporation of oxygen into the cluster structure, further complicating unambiguous structure prediction.
Original language | English |
---|---|
Pages (from-to) | 3581-3589 |
Number of pages | 9 |
Journal | Journal of Physical Chemistry C |
Volume | 118 |
Issue number | 7 |
DOIs | |
Publication status | Published - 20 Feb 2014 |