Self-Poisoning Dynamical Effects in the Oxygen Reduction Reaction on Pt(111) from a Top-Down Kinetic Analysis

A kinetic analysis of the oxygen reduction reaction (ORR) on Pt(111) is performed from available experimental data and is checked against first-principles results. We find that although the ORR proceeds mainly through the associative pathway, the dissociative pathway may play a key role in poisoning the catalyst surface prior to steady state. The present analysis, therefore, highlights the potential significance of dynamical effects inside the ORR, which motivates the fast development of highly space- and time-resolved probing techniques.