Role of Lattice Oxygen in the Oxygen Evolution Reaction on Co₃O₄: Isotope Exchange Determined Using a Small-Volume...

This work demonstrates the role of lattice oxygen of metal oxide catalysts in the oxygen evolution reaction (OER) as evidenced by isotope labeling together with the differential electrochemical mass spectrometry (DEMS) method. Our recent report assessed this role for Co₃O₄ using a flow-through DEMS cell, which requires a large volume of electrolyte. Herein, we extend this procedure to different Co₃O₄ catalyst loadings and particle sizes as well as the mixed Ag + Co₃O₄ catalyst. We introduce, for the first time, a novel small-volume DEMS cell design capable of using disc electrodes and only <0.5 mL of electrolyte. The reliability of the cell is demonstrated by monitoring gas evolution during OER in real time. This cell shows high sensitivity, high collection efficiency, and very short delay time. DEMS results reveal that only the interfacial part (∼0.2% of the total loading or 25% of surface atoms) of the catalyst is active for OER. Interestingly, the amount of oxygen exchanged on the mixed Ag + Co₃O₄ catalyst is higher than that on the single Co₃O₄ catalyst, which illustrates the improved electrocatalytic activity previously reported on this mixed catalyst. Furthermore, the real surface area of the catalysts is estimated using different methods (namely, the ball model, double layer capacitance, isotope exchange, and redox peak methods). The surface areas estimated from the Brunauer-Emmett-Teller (BET) and ball models are comparable but roughly three times higher than that of the redox peak method. Our method represents an alternative approach for probing the mechanism and real surface area of catalysts.