Enhancing the Intrinsic Activity and Stability of Perovskite Cobaltite at Elevated Temperature Through Surface Stress

Perovskite-based oxides attract great attention as catalysts for energy and environmental devices. Nanostructure engineering is demonstrated as an effective approach for improving the catalytic activity of the materials. The mechanism for the enhancement, nevertheless, is still not fully understood. In this study, it is demonstrated that compressive strain can be introduced into freestanding perovskite cobaltite La_0.8 Sr_0.2 CoO_{3- δ} (LSC) nanofibers with sufficient small size. Crystal structure analysis suggests that the LSC fiber is characterized by compressive strain along the ab plane and less distorted CoO₆ octahedron compared to the bulk powder sample. Accompanied by such structural changes, the nanofiber shows significantly higher oxygen reduction reaction (ORR) activity and better stability at elevated temperature, which is attributed to the higher oxygen vacancy concentration and suppressed Sr segregation in the LSC nanofibers. First-principle calculations further suggest that the compressive strain in LSC nanofibers effectively shortens the distance between the Co 3d and O 2p band center and lowers the oxygen vacancy formation energy. The results clarify the critical role of surface stress in determining the intrinsic activity of perovskite oxide nanomaterials. The results of this work can help guide the design of highly active and durable perovskite catalysts via nanostructure engineering.