Differentiating Oxygen Exchange Reaction Mechanisms across Phase Boundaries.

Triggering phase transitions by controlling the anion stoichiometry is an effective method of tuning the electrocatalytic activity of the functional oxides. However, understanding the potential differences in the reaction mechanism(s) of different phases requires the accurate mapping of phase boundaries during the electrochemical reactions, which can be quite challenging. In this work, we have established a feasible electrochemical method based on the measurement of chemical capacitance to resolve the critical stoichiometry at phase boundaries under operando conditions. We select a simple binary oxide PrO x as a proof-of-principle model system, which shows excellent activity for high-temperature oxygen incorporation and evolution reactions (OIR/OER). We show that the phase transition can be sensitively probed by quantifying the chemical capacitance, which can be further used for differentiating the OIR/OER mechanisms across the phase boundary of PrO x . Therefore, our findings provide a new framework for exploring phase engineering as a tool for the design of electrocatalysts.