Leveraging Iron in the Electrolyte to Improve Oxygen Evolution Reaction Performance: Fundamentals, Strategies, and Perspectives

Abstract Electrochemical water splitting is a pivotal technology for storing intermittent electricity from renewable sources into hydrogen fuel. However, its overall energy efficiency is impeded by the sluggish oxygen evolution reaction (OER) at the anode. In the quest to design high‐performance anode catalysts for driving the OER under non‐acidic conditions, iron (Fe) has emerged as a crucial element. Although the profound impact of adventitious electrolyte Fe n+ species on OER catalysis had been reported forty years ago, recent interest in tailoring the electrode‐electrolyte interface has spurred studies on the controlled introduction of Fe ions into the electrolyte to improve OER performance. During the catalytic process, scenarios where the rate of Fe n+ deposition on a specific host material outruns that of dissolution pave the way for establishing highly efficient and dynamically stable electrochemical interfaces for long‐term steady operation. This review systematically summarizes recent endeavors devoted to elucidating the behaviors of in situ Fe (aq.) incorporation, the role of incorporated Fe sites in the OER, and critical factors influencing the interplay between the electrode surface and Fe ions in the electrolyte environment. Finally, unexplored issues related to comprehensively understanding and leveraging the dynamic exchange of Fe n+ at the interface for improved OER catalysis are summarized.