Systematic Control of Redox Properties and Oxygen Reduction Reactivity through Colloidal Ligand-Exchange Deposition of Pd on Au.

Core-shell nanoparticles of Au@Pd with precise submonolayer, monolayer, or multilayer structure were synthesized using ligand-exchange reactions of palladate ions onto colloidal Au nanocrystals. Decoupling the palladate adsorption step from the subsequent reduction enables excellent precision, uniformity, and tunability in the Pd shell thickness. The redox properties of the surface Pd are directly correlated to the thickness of the Pd shell with a >+200 mV shift in the PdO reduction potential for submonolayer Au@Pd nanoparticles compared to pure Pd. Using these precisely controlled core-shell materials, the oxygen reduction catalytic activity can be directly correlated to PdO reduction potential and Pd surface coverage on Au. When the Pd oxide reduction peak is shifted by +240 mV compared to pure Pd, a 50 mV reduction in overpotential and a 4-fold increase in kinetic current density for oxygen reduction are observed. Colloidal ligand-exchange synthesis may be particularly useful for noble metal core-shell catalysts as a strategy to subtly tune the electronic properties of surface atoms in order to lower overpotential and increase catalytic turnover.