Mechanisms of Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction on High-Index Platinum n(111)–(111) Surfaces

Abstract

Oxygen reduction reactions (ORRs) on high-index planes of Pt n(111)-(111) were studied by density functional theory (DFT). The stepped surfaces, where n = 2, 3, and 4, showed that O2, O, and OH exhibited higher binding energies along the step compared to the terrace plane. The Pt atoms along the step can become distorted through the binding of the O and OH, where the shift in position of the Pt atoms is the largest along the stepped sites, hence forming stronger bonds with O atoms. One of the two O atoms produced from the bond dissociation of O2 will push the other one down a step with lower binding energies, consequently reducing the energy required for the protonation reaction (O + H(+) → OH, and OH + H(+) → H2O). The quicker recovery back to the clean Pt surface would therefore improve the catalytic properties of Pt nanoparticles, especially those with exposure to high-indexed facets.