Molecular Origin of the Selectivity Differences between Palladium and Gold–Palladium in Benzyl Alcohol Oxidation: Different Oxygen Adsorption Properties

The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. The calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.