Bimetallic PdAu catalysts are more active than monometallic ones for the selective oxidation of alcohols, but the reasons for improvement remain insufficiently detailed. A metal-on-metal material can probe the structure–catalysis relationship more clearly than conventionally prepared bimetallics. In this study, Pd-on-Au nanoparticles with variable Pd surface coverages (sc%) ranging from 10 to 300 sc% were synthesized and immobilized onto carbon (Pd-on-Au/C). Tested for glycerol oxidation at 60 °C, pH 13.5, and 1 atm under flowing oxygen, the series of Pd-on-Au/C materials showed volcano-shape catalytic activity dependence on Pd surface coverage. Increasing surface coverage led to higher catalytic activity, such that initial turnover frequency (TOF) reached a maximum of ∼6000 h−1 at 80 sc%. Activity decreased above 80 sc% mostly due to catalyst deactivation. Pd-on-Au/C at 80 sc% was >10 times more active than monometallic Au/C and Pd/C, with both exhibiting TOF values less than ∼500 h−1. Glyceric acid was the dominant primary reaction product for all compositions, with its zero-conversion selectivity varying monotonically as a function of Pd surface coverage. Glyceric acid yield from Pd-on-Au/C (80 sc%) was 42%, almost double the yields from Au/C and Pd/C (16% and 22%, respectively). Ex situ X-ray absorption near edge structure analysis of two Pd-on-Au/C materials with comparable activities (60 sc% and 150 sc%) showed that the former had less oxidized Pd ensembles than the latter, and that both catalysts were less oxidized compared to Pd/C. That Au stabilizes the metallic state of surface Pd atoms may be responsible for activity enhancement observed in other PdAu-catalyzed oxidation reactions. Decorating a Au surface with Pd generates a catalyst that has the deactivation resistance of Au, the higher glyceric acid selectivity of Pd, and the synergistically higher activities that neither metal has.
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