Engineering surface segregation of perovskite oxide through wet exsolution for CO catalytic oxidation

Cation segregation occurring near the surface or interfaces of solid catalysts plays an important role in catalytic reactions. Unfortunately, the native surface of perovskite oxides is dominated by passivated A-site segregation, which severely hampers the catalytic activity and durability of the system. To address this issue, herein, we present a wet exsolution method to reconstruct surface segregation in perovskite cobalt oxide. Under reduction etching treatment of glycol solution, inert surface Sr segregation was transformed into active Co₃O₄ segregation. By varying the reaction time, we achieved differing coverage of the active Co₃O₄ segregation on the La_0.5Sr_0.5CoO_3-δ (LSCO) perovskite oxide surface. This study reveals that CO oxidation activity exhibits a volcano-shaped dependence on the coverage of Co₃O₄ segregation at the surface of a perovskite cobalt oxide. Furthermore, we find that a suitable coverage of Co₃O₄ segregation can dramatically improve the catalytic activity of the perovskite catalyst by enhancing interface interactions. Co K-edge, Co L-edge, and O K-edge X-ray absorption spectra confirm that the synergistic effect optimizes the covalence of the metal-oxygen bond at the surface and interface. This work not only contributes to the design and development of perovskite-type catalysts, but also provides important insight into the relationship between surface segregation and catalytic activity.