Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation.

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al O and SiO . High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al O and SiO . In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al O and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al O than those in Pd supported on SiO , which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm ) reacted first with oxygen in the case of CO-saturated Pd on Al O and SiO , which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.