Pd 4d Orbital Overlapping Modulation on Au@Pd Nanowires for Efficient H₂O₂ Production

Isolating Pd atoms has been shown to be crucial for the design of a Pd-based electrocatalyst toward 2e(-) oxygen reduction reaction (ORR). However, there are limited studies focusing on the systematic compositional design that leads to an optimal balance between activity and selectivity. Herein, we design a series of Au@Pd core@shell structures to investigate the influence of the Pd 4d orbital overlapping degree on 2e(-) ORR performance. Density functional theory (DFT) calculations indicate that enhanced H2O2 selectivity and activity are achieved at Pd n clusters with n <= 3, and Pd clusters larger than Pd-3 should be active for 4e(-) ORR. However, experimental results show that Au@Pd nanowires (NWs) with Pd-4 as the primary structure exhibit the optimal H2O2 performance in an acidic electrolyte with a high mass activity (7.05 A mg(-1) at 0.4 V) and H2O2 selectivity (nearly 95%). Thus, we report that Pd4, instead of Pd-3, is the upper threshold of Pd cluster size for an ideal 2e(- )ORR. It results from the oxygen coverage on the catalyst surface during the ORR process, and such an oxygen coverage phenomenon causes electron redistribution and weakened *OOH binding strength on active sites, leading to enhanced activity of Pd-4 with only 0.06 V overpotential in acidic media.