Elucidation of the Oxygen Reduction Volcano in Alkaline Media using a Copper-Platinum(111) Alloy

The relationship between the binding of the reaction intermediates and oxygen reduction activity in alkaline media was experimentally explored. By introducing Cu into the 2nd surface layer of a Pt(111) single crystal, the surface reactivity was tuned. In both 0.1(M) NaOH and 0.1(M) KOH, the optimal catalyst should exhibit OH binding circa 0.1 eV weaker than Pt(111), via a Sabatier volcano; this observation suggests that the reaction is mediated via the same surface bound intermediates as in acid, in contrast to previous reports. In 0.1(M) KOH, the alloy catalyst at the peak of the volcano exhibits a maximum activity of 10 ± 8 mAcm² at 0.9 V vs. a reversible hydrogen electrode (RHE). This activity constitutes a circa 60-fold increase over Pt(111) in 0.1(M) HClO₄.