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.