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 H2 and O2 on a PdAu alloy surface based on periodic density functional theory calculations. Our calculations demonstrate that H2O2 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 H2O2 formation on PdAu alloys compared to that on the monometallic Pd and Au counterparts.