Tailoring Ion Ordering in Perovskite Oxide for High‐Temperature Oxygen Evolution Reaction

Abstract Perovskites exhibit excellent high‐temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2−xFexO5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A‐site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A‐site‐ordered and oxygen‐vacancy‐disordered PrBaCo2O5+δ anode exhibits the highest performance of 3.40 A cm−2 at 800 °C and 2.0 V. This work sheds light on the critical role of ion orderings in the high‐temperature OER performance and paves a new way for screening novel anode materials of SOECs.