10.1021/jp4040437.s001 Anna V. Beletskaya Anna V. Beletskaya Daria A. Pichugina Daria A. Pichugina Alexander F. Shestakov Alexander F. Shestakov Nikolay E. Kuz’menko Nikolay E. Kuz’menko Formation of H<sub>2</sub>O<sub>2</sub> on Au<sub>20</sub> and Au<sub>19</sub>Pd Clusters: Understanding the Structure Effect on the Atomic Level American Chemical Society 2016 palladium doping effects 19Pd structure features H 2. Size DFT H 2O H 2O H 2O H 2O synthesis OOH H 2O production H 2O formation Atomic LevelSupported gold nanoparticles OH 2016-02-19 01:38:47 Journal contribution https://acs.figshare.com/articles/journal_contribution/Formation_of_H_sub_2_sub_O_sub_2_sub_on_Au_sub_20_sub_and_Au_sub_19_sub_Pd_Clusters_Understanding_the_Structure_Effect_on_the_Atomic_Level/2389060 Supported gold nanoparticles are promising catalysts for production of H<sub>2</sub>O<sub>2</sub> from O<sub>2</sub> and H<sub>2</sub>. Size, structure, and palladium doping effects play the key role in activity and selectivity of a gold catalyst. We performed a study of the influence of Au<sub>20</sub> and Au<sub>19</sub>Pd structure features on the main steps of H<sub>2</sub>O<sub>2</sub> formation on the atomic level, using the DFT/PBE approach with relativistic all electron basis set. The top, edge, and facet atoms of the tetrahedral Au<sub>20</sub> cluster as well as a palladium atom of Au<sub>19</sub>Pd located on the top, edge, and facet of a tetrahedron have been considered as active sites of steps involved in H<sub>2</sub>O<sub>2</sub> synthesis. The thermodynamic and kinetic data including Gibbs free energies and the activation Gibbs free energies were calculated for the steps determining the formation of H<sub>2</sub>O<sub>2</sub> (H<sub>(s)</sub> + OOH<sub>(s)</sub> = H<sub>2</sub>O<sub>2(s)</sub>, H<sub>2</sub>O<sub>2(s)</sub> = H<sub>2</sub>O<sub>2(g)</sub>) and for one step decreasing the selectivity (H<sub>2</sub>O<sub>2(s)</sub> = OH<sub>(s)</sub> + OH<sub>(s)</sub>). Gold tends to have low activity and high selectivity in H<sub>2</sub>O<sub>2</sub> synthesis regardless of the structure of active site. Low coordinated palladium atoms promote H<sub>2</sub>O<sub>2</sub> formation as well as its dissociation. Pd on a facet of a cluster facilitates H<sub>2</sub>O<sub>2</sub> production with high activity and selectivity.