1 Department of Physics, Technical University of Denmark2 Theoretical Atomic-scale Physics, Department of Physics, Technical University of Denmark3 Stanford University4 Center for Atomic-scale Materials Design, Center, Technical University of Denmark5 SLAC National Accelerator Laboratory6 Stanford University
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.
Journal of Physical Chemistry Letters, 2012, Vol 3, Issue 20, p. 2948-2951