Modes of Fe Incorporation in Co–Fe (Oxy)hydroxide Oxygen Evolution Electrocatalysts

Ni–Fe (oxy)hydroxide and Co–Fe (oxy)hydroxide are among the most active oxygen evolution reaction (OER) catalysts in alkaline media. Fe is essential for the high activity, but the details of how Fe is incorporated into the Ni or Co (oxy)hydroxide structure and affects catalysis remain incompletely understood. This study concerns two different modes of Fe incorporation to form Co(Fe)OxHy, which both yield increased OER activity but result in Fe and Co species that differ in chemical reactivity and electrochemical response. Co(Fe)OxHy films that were cathodically deposited from mixed Co and Fe nitrate solution (co‐deposited) result in Fe species that interact strongly with the Co species (as evidenced by an anodic shift in the Co redox wave) and are difficult to leach out under electrochemical conditions. Fe incorporated into a CoOxHy film by cycling in Fe‐spiked KOH electrolyte similarly enhance activity, but do not strongly electronically interact with the majority of the Co in the film and are removed by cycling in Fe‐free KOH. These results support the hypothesis that co‐deposition of Co(Fe)OxHy leads to films where the Co and Fe are mixed within the nanosheet structure and cycling in Fe‐spiked KOH incorporates Fe species largely at surface, edge, or defect sites, where they drive OER but do not otherwise significantly modulate the electrochemical response of the Co. À la mode: Fe can be incorporated in different environments in CoOxHy oxygen‐evolution catalysts to increase activity. Fe that is rapidly incorporated into the Co oxyhydroxide from Fe cations in solution (likely at edges or defects) enhances activity. Fe substituting for bulk Co modulates the observed Co voltammetry.