Formic Acid Oxidation on Pd Thin Film Coated Au Nanocrystals

Cubic, octahedral, and rhombic dodecahedral gold nanocrystals enclosed by {100}, {111}, and {110} facets, respectively, were prepared by a seed-mediated growth method at the room temperature. Palladium thin films were coated on these Au nanocrystals by a redox replacement approach to explore their catalytic activities. It is revealed that formic acid and carbon monoxide oxidation in 0.1 M HClO4 on Au nanocrystals coated with one monolayer (ML) of Pd are facet-dependent and resemble those obtained from corresponding Pd single crystals and Pd films deposited on bulk Au single crystals, suggesting epitaxial growth of Pd overlayers on the Au nanocrystal surfaces. As the Pd film thickness increased, formic acid oxidation current density decreased and the CO oxidation potential moved to more negative. The catalytic activity remained largely unchanged after 3–5 MLs of Pd deposition. The specific adsorption of (bi)sulfate was shown to hinder the formic acid oxidation and the effect decreased with the increasing Pd film thickness. These observations were explained in the framework of the d-band theory. This study highlights the feasibility of engineering high-performance catalysts through deposition of catalytically active metal thin films on facet-controlled inert nanocrystals.