Active Motif Change of Ni‐Fe Spinel Oxide by Ir Doping for Highly Durable and Facile Oxygen Evolution Reaction

Abstract

Abstract The oxygen evolution reaction (OER) is crucial for producing sustainable energy carriers. Herein, Ir (5 mol.%) doped inverse‐spinel NiFe 2 O 4 (Ir‐NFO) nanoparticles deposited on Ni foam (NF) by scalable solution casting are considered a promising OER electrocatalyst for industrial deployments. The Ir‐NFO/NF (with minimal lattice distortion by uniform Ir doping) provides an OER overpotential of 251 mV (intrinsically outperforming NFO/NF and benchmarking IrO 2 /NF) and extraordinary robustness over 130 days at 100 mA cm −2 . In situ X‐ray absorption spectroscopy reveals oxidation only for Fe on NFO, whereas concurrent generation of higher‐valent Ni and Fe occurs on Ir‐NFO during OER. Density functional theory calculations further demonstrate that Ir substitutes the sublayer Ni octahedral site and switches the main active reaction center from Fe Oh Fe Td bridge site (FeOFe) on NFO to Ni Oh –Fe Td bridge site (NiOFe active motif) on Ir‐NFO for a co‐catalytic OER. This study sheds new light on precious‐metal doped Ni‐Fe oxides, which may be applicable to other binary/ternary oxide electrocatalysts.