Tuning the Activity of Silver Alloys for the Oxygen Reduction Reaction in Alkaline Media

High Resolution Image Download MS PowerPoint Slide Ag-based catalysts have recently attracted much attention as potential candidates to substitute costly Pt-based electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. Although the electrocatalytic activity of Pt-based alloys is known to exhibit a strong dependence on their electronic structures, a relationship between electronic structure and the ORR mechanism in Ag-based alloys still remains to be elucidated. Herein, by means of physical vapor deposition, we prepare Ag binary thin films (CoAg, CuAg, AuAg, and FeAg) with well-controlled compositions as a tool to investigate the ORR mechanism on Ag surfaces. The bimetallic thin films are evaluated for their ORR performance in alkaline media, and their specific activity at 0.8 V RHE is shown to correlate with the Ag electronic structure. Even though all thin films show different responses to potential cycling, all bimetallic samples exhibit a surface Ag enrichment after ORR. It is shown that the ORR occurs through different mechanisms on these Ag-rich surfaces, which in turn is potential-dependent. Tafel slopes reveal faster ORR kinetics at low overpotentials on all surfaces, whereas only CuAg surpasses pure Ag at higher overpotentials. Moreover, despite their incomplete O 2 reduction, CuAg and AuAg exhibit an overall superior ORR activity over pure Ag, with a more than 2-fold increase in specific activity at 0.8 V RHE attributed to enhancements originating from electronic effects and surface defects, respectively. Since the potential-dependent improved ORR mechanism observed for Ag bimetallic samples makes a rational design of Ag-based electrocatalysts difficult, these results aim to provide insights for a more tailored design of electrocatalysts by shedding light on the mechanisms through which the ORR kinetics are improved on Ag surfaces in alkaline media.