Unifying the 2e<sup>–</sup> and 4e<sup>–</sup> Reduction of Oxygen on Metal Surfaces
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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<sup>–</sup> versus 4e<sup>–</sup> 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, Δ<i>G</i><sub>OH*</sub>, the free energy of adsorbed OH*, can be
used to describe trends for the 2e<sup>–</sup> and 4e<sup>–</sup> reduction of oxygen. While the weak binding of OOH* on Au(111) makes
it an unsuitable catalyst for the 4e<sup>–</sup> reduction,
this weak binding is optimal for the 2e<sup>–</sup> reduction
to H<sub>2</sub>O<sub>2</sub>. We find quite a remarkable agreement
between the predictions of the model and experimental results spanning
nearly 30 years