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Updated: Apr 5, 2026

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Unifying the 2e(-) and 4e(-) Reduction of Oxygen on Metal Surfaces
Venkatasubramanian Viswanathan, Heine Anton Hansen, Jan Rossmeisl1
1§Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, DK-2800, Lyngby, Denmark.
Abstract:
Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e(-) versus 4e(-) reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e(-) and 4e(-) reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e(-) reduction, this weak binding is optimal for the 2e(-) reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.
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