On the Role of Pd Ensembles in Selective H2O2 Formation on PdAu Alloys

We present the role of Pd ensembles in the selective direct synthesis of H2O2 from H-2 and O-2 on a PdAu alloy surface based on periodic density functional theory calculations. Our calculations demonstrate that H2O2 fort-nation 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 H2O2 formation on PdAu alloys compared to that on the monometallic Pd and Au counterparts.