On the role of Pd ensembles in selective H ₂O ₂ formation on PdAu alloys

We present the role of Pd ensembles in the selective direct synthesis of H ₂O ₂ from H ₂ and O ₂on a PdAu alloy surface based on periodic density functional theory calculations. Our calculations demonstrate that H ₂O ₂ formation is strongly affected by the spatial arrangement of Pd and Au surface atoms. In particular, Pd monomers surrounded by less active Au atoms that suppress O-O bond scission are primarily responsible for the significantly enhanced selectivity toward H ₂O ₂ formation on PdAu alloys compared to that on the monometallic Pd and Au counterparts.