KIr₄O₈ Nanowires with Rich Hydroxyl Promote Oxygen Evolution Reaction in Proton Exchange Membrane Water Electrolyzer

Abstract The sluggish kinetics for anodic oxygen evolution reaction (OER) and insufficient catalytic performance over the corresponding Ir‐based catalysts are still enormous challenges in proton exchange membrane water electrolyzer (PEMWE). Herein, it is reported that KIr₄O₈ nanowires anode catalyst with more exposed active sites and rich hydroxyl achieves a current density of 1.0 A cm⁻² at 1.68 V and possesses excellent catalytic stability with 1230 h in PEMWE. Combining in situ Raman spectroscopy and differential electrochemical mass spectroscopy results, the modified adsorbate evolution mechanism is proposed, wherein the rich hydroxyl in the inherent structure of KIr₄O₈ nanowires directly participates in the catalytic process for favoring the OER. Density functional theory calculation results further suggest that the enhanced proximity between Ir (d) and O (p) band center in KIr₄O₈ can strengthen the covalence of Ir–O, facilitate the electron transfer between adsorbents and active sites, and decrease the energy barrier of rate‐determining step from OH^* to O^* during the OER.