Concurrent Amorphization and Nanocatalyst Formation in Cu-Substituted Perovskite Oxide Surface: Effects on Oxygen Reduction Reaction at Elevated Temperatures

The activity and durability of chemical/electrochemical catalysts are significantly influenced by their surface environments, highlighting the importance of thoroughly examining the catalyst surface. Here, Cu-substituted La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ is selected, a state-of-the-art material for oxygen reduction reaction (ORR), to explore the real-time evolution of surface morphology and chemistry under a reducing atmosphere at elevated temperatures. Remarkably, in a pioneering observation, it is discovered that the perovskite surface starts to amorphize at an unusually low temperature of approximately 100 °C and multicomponent metal nanocatalysts additionally form on the amorphous surface as the temperature raises to 400 °C. Moreover, this investigation into the stability of the resulting amorphous layer under oxidizing conditions reveals that the amorphous structure can withstand a high-temperature oxidizing atmosphere (≥650 °C) only when it has undergone sufficient reduction for an extended period. Therefore, the coexistence of the active nanocatalysts and defective amorphous surface leads to a nearly 100% enhancement in the electrode resistance for the ORR over 200 h without significant degradation. These observations provide a new catalytic design strategy for using redox-dynamic perovskite oxide host materials.