Cation-Deficient Perovskites Greatly Enhance the Electrocatalytic Activity for Oxygen Reduction Reaction

Many perovskite oxides (ABO₃ ) are considered the most promising alternatives to noble metal catalysts for oxygen reduction reaction (ORR) due to their high intrinsic activities. However, their electrocatalytic performance is often limited by poor electrical conductivity and low specific surface area. Here an electrochemically induced calcium-leaching process is reported to greatly increase the electrochemical surface area (ECSA) of La_0.6 Ca_0.4 MnO₃ (LCMO64). The ECSA of the activated, Ca-deficient LCMO64 is ≈33.84% higher than that of the unactivated materials, demonstrating superior electrocatalytic ORR performance to the benchmark commercial Pt/C catalyst in an alkaline solution. Theoretical analysis coupled with electrochemical surface state probing and pH-dependent microkinetic modeling suggests that this catalyst with the identified most favorable state under ORR operating conditions reaches the Sabatier optimum of alkaline ORR. This reconstructed LCMO64 is among the best-performing ORR catalysts ever reported, providing new insights into the design of advanced perovskite materials with optimal surface chemistry.