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

Angewandte Chemie 2018 January 19
Herein we experimentally explore the relationship between the binding of the reaction intermediates and oxygen reduction activity in alkaline media. By introducing Cu into the 2nd surface layer of a Pt(111) single crystal, we tune the surface reactivity. We demonstrate that in both NaOH and KOH, the optimal catalyst should exhibit OH binding ~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 101±8 mA/cm2 at 0.9 V vs. a reversible hydrogen electrode (RHE). This activity constitutes a ~60-fold increase over Pt(111) in 0.1 M HClO4.

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