Enhanced Hot Electron Flow and Catalytic Synergy by Engineering Core-Shell Structures on Au-Pd Nanocatalysts.

The synergistic catalytic performances of bimetallic catalysts are often attributed to the reaction mechanism associated with the alloying process of the catalytic metals. Chemically induced hot electron flux is strongly correlated with catalytic activity, and the interference between two metals at the atomic level can have a huge impact on the hot electron generation on the bimetallic catalysts. In this study, we investigate the correlation between catalytic synergy and hot electron chemistry driven by the electron coupling effect using a model system of Au-Pd bimetallic nanoparticles. We show that the bimetallic nanocatalysts exhibit enhanced catalytic activity under the hydrogen oxidation reaction compared with that of monometallic Pd nanocatalysts. Analysis of the hot electron flux generated in each system revealed the formation of Au/PdO interfaces, resulting in high reactivity on the bimetallic catalyst. In further experiments with engineering the Au@Pd core-shell structures, we reveal that the hot electron flux, when the topmost surface Pd atoms were less affected by inner Au, due to the concrete shell, was smaller than the alloyed one. The alloyed bimetallic catalyst forming the metal-oxide interfaces has a more direct effect on the hot electron chemistry, as well as on the catalytic reactivity. The great significance of this study is in the confirmation that the change in the hot electron formation rate with the metal-oxide interfaces can be observed by shell engineering of nanocatalysts.