Activity trends of binary silver alloy nanocatalysts for oxygen reduction reaction in alkaline media

The electrocatalytic activity of Pt-based alloys exhibits a strong dependence on their electronic structures, but a relationship between electronic structure and oxygen reduction reaction (ORR) activity in Ag-based alloys is still not clear. Here, a vapor deposition based approach is reported for the preparation of Ag₇₅M₂₅ (M = Cu, Co, Fe, and In) and Ag_xCu_{100- x} (x = 0, 25, 45, 50, 55, 75, 90, and 100) nanocatalysts and their electronic structures are determined by valence band spectra. The relationship of the d-band center and ORR activity exhibits volcano-shape behaviors, where the maximum catalytic activity is obtained for Ag₇₅Cu₂₅ alloys. The ORR enhancement of Ag₇₅Cu₂₅ alloys originates from the 0.12 eV upshift in d-band center relative to pure Ag, which is different from the downshift in the d-band center in Pt-based alloys. The activity trend for these Ag₇₅M₂₅ alloys is in the order of Ag₇₅Cu₂₅ > Ag₇₅Fe₂₅ > Ag₇₅Co₂₅. These results provide an insight to understand the activity and stability enhancement of Ag₇₅Cu₂₅ and Ag₅₀Cu₅₀ catalysts by alloying.