Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)–electrodes: Effects of the heteroatomic junction on the reaction paths

ARCE, M.; BELLETTI, G.; SCHULTE, E.; QUAINO, P.

APPLIED SURFACE SCIENCE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2018 vol. 441 p. 663 - 669

0169-4332

The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due toits implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt,Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic(100) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associativeand dissociative, were considered for the orr. Changes in the electronic properties of these materialswith respect to the pure metals were acknowledged to gain understanding in the overall reactivitytrend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluatedby means of geometrical and energetic parameters; being the intermediates preferably adsorbedon Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals.Finally, the kinetics of the OAO bond breaking in O2 and OOH adsorbed intermediates in the bimetallicmaterials and the influence of the Au-M junction were studied by means of the nudge elastic-bandmethod. A barrierless process for the scission of O2 was found in Au-M for the higher M ratios.Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggestinga highly reactive surface towards the orr. The OAO scission of the OOH was found to be a barrierlessprocess in AuAPt systems and nearly barrierless in all AuAPd systems, implying that thereduction ofO2 in these systems proceeds via the full reduction of O2 to H2O, avoiding H2O2 formation.