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 La0.6Sr0.4Co0.2Fe0.8O3-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.

Revitalizing Oxygen Reduction Reactivity of Composite Oxide Electrodes via Electrochemically Deposited PrOx Nanocatalysts.

Solid oxide fuel cells that operate at intermediate temperatures require efficient catalysts to enhance the inherently poor electrochemical activity of the composite electrodes. Here, a simple and practical electrochemical deposition method is presented for fabricating a PrOx overlayer on lanthanum strontium manganite-yttria-stabilized zirconia (LSM-YSZ) composite electrodes. The method requires less than four minutes for completion and can be carried out under at ambient temperature and pressure. Crucially, the treatment significantly improves the electrode's performance without requiring heat treatment or other supplementary processes. The PrOx-coated LSM-YSZ electrode exhibits an 89% decrease in polarization resistance at 650 °C (compared to an untreated electrode), maintaining a tenfold reduction after ≈400 h. Transmission line model analysis using impedance spectra confirms how PrOx coating improved the oxygen reduction reaction activity. Further, tests with anode-supported single cells reveal an outstanding peak power density compared to those of other LSM-YSZ-based cathodes (e.g., 418 mW cm-2 at 650 °C). Furthermore, it is demonstrated that multicomponent coating, such as (Pr,Ce)Ox, can also be obtained with this method. Overall, the observations offer a promising route for the development of high-performance solid oxide fuel cells.