Iron‐Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation

Abstract The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non‐noble metal‐based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three‐dimensional (3D) nanoflower‐like electrocatalyst (CFMO) via a simple one‐step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O−O radical coupling for enhanced O 2 evolution. The optimized CFMO‐2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm −2 , alongside exceptional long‐term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal‐based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO‐2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm −2 . In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First‐principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non‐noble metal‐based electrocatalysts and the development of AEMWE.