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

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 O₂ 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.