In Situ Activation Endows Orthorhombic Fluorite-Type Samarium Iridium Oxide with Enhanced Acidic Water Oxidation.

Developing electrochemical catalysts for acidic water oxidation with improved activity and stability has been the key to the further popularization of proton exchange membrane electrolyzers. In this work, an orthorhombic fluorite-type samarium iridium oxide (Sm3IrO7) catalyst is synthesized by a simple solid-state reaction. After in situ activation, the as-prepared Sm3IrO7 exhibits higher mass activity and durability than that of commercial IrO2. The in-depth analyses indicate the formation of amorphous IrOx species on the surface to evolve to a new heterostructure IrOx/Sm3IrO7, along with Sm leaching during the in situ activation process. More importantly, strong electronic interactions exist between newborn IrOx species and remaining Sm3IrO7, leading to the compressed Ir-O bonds in IrOx compared to commercial IrO2, thus reducing the energy barrier for oxygen evolution reaction (OER) intermediates to improve the OER process. Based on the above-mentioned analyses, it is speculated that the actual active species for enhanced acidic water oxidation should be IrOx/Sm3IrO7, rather than Sm3IrO7 itself. Theoretical calculations confirm that the optimal energy level path of IrOx/Sm3IrO7 follows the lattice oxygen mechanism, and the energy level of surface Ir 5d orbitals is lower than O 2p orbitals in IrOx/Sm3IrO7, enabling it a superior OER activity.