A Dissolution/Precipitation Equilibrium on the Surface of Iridium‐Based Perovskites Controls Their Activity as Oxygen Evolution Reaction Catalysts in Acidic Media

Recently, IrV‐based perovskite‐like materials were proposed as oxygen evolution reaction (OER) catalysts in acidic media with promising performance. However, iridium dissolution and surface reconstruction were observed, questioning the real active sites on the surface of these catalysts. In this work, Sr2MIr(V)O6 (M=Fe, Co) and Sr2Fe0.5Ir0.5(V)O4 were explored as OER catalysts in acidic media. Their activities were observed to be roughly equal to those previously reported for La2LiIrO6 or Ba2PrIrO6. Coupling electrochemical measurements with iridium dissolution studies under chemical or electrochemical conditions, we show that the deposition of an IrOx layer on the surface of these perovskites is responsible for their OER activity. Furthermore, we experimentally reconstruct the iridium Pourbaix diagram, which will help guide future research in controlling the dissolution/precipitation equilibrium of iridium species for the design of better Ir‐based OER catalysts. Dissolution/precipitation equilibrium: By coupling electrochemical measurements with iridium dissolution studies, it is shown that the deposition of an IrOx layer on the surface of IrV‐based perovskites is responsible for their OER activity. The iridium Pourbaix diagram is reconstructed to help guide future research in controlling the dissolution/precipitation equilibrium of iridium species for the design of better Ir‐based OER catalysts.