Unusual Activity Trend for CO Oxidation on Pd(x)Au(140-x)@Pt Core@Shell Nanoparticle Electrocatalysts.
A theoretical and experimental study of the electrocatalytic oxidation of CO on PdxAu140-x@Pt dendrimer-encapsulated nanoparticle (DEN) catalysts is presented. These nanoparticles are comprised of a core having an average of 140 atoms and a Pt monolayer shell. The CO oxidation activity trend exhibits an unusual koppa shape as the number of Pd atoms in the core is varied from 0 to 140. Calculations based on density functional theory suggest that the koppa-shaped trend is driven primarily by structural changes that affect the CO binding energy on the surface. Specifically, a pure Au core leads to deformation of the Pt shell and a compression of the Pt lattice. In contrast, Pd, from the pure Pd cores, tends to segregate on the DEN surface, forming an inverted configuration having Pt within the core and Pd in the shell. With a small addition of Au, however, the alloy PdAu cores stabilize the core@shell structures by preventing Au and Pd from escaping to the particle surface.
†Department of Chemistry, ‡Texas Materials Institute, and §Institute for Computational and Engineering Sciences, The University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Long
L
Luo
†Department of Chemistry, ‡Texas Materials Institute, and §Institute for Computational and Engineering Sciences, The University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Liang
L
Zhang
†Department of Chemistry, ‡Texas Materials Institute, and §Institute for Computational and Engineering Sciences, The University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Graeme
G
Henkelman
†Department of Chemistry, ‡Texas Materials Institute, and §Institute for Computational and Engineering Sciences, The University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Richard M
RM
Crooks
CO oxidation; Cu UPD; DFT; PdAu; PdAu@Pt; core@shell; deformation