Dynamic Coordination Chemistry‐Driven Amorphous NiCoFe Oxyhydroxide Core‐Shell Nanowires With High‐Valence Metal Sites for High‐Performance Oxygen Evolution Catalysis

Abstract The anodic oxygen evolution reaction (OER) is acknowledged as the kinetic constraint in water electrolysis. Amorphous (oxy)hydroxides containing metal ions in high valence states can accelerate reaction kinetics with considerable intrinsic activity; yet they face thermodynamic hurdles of formation. Here, we present a dynamic coordination chemistry approach utilizing metal‐organic frameworks (MOFs) to fabricate core‐shell heterostructured catalysts, consisting of amorphous NiCoFe oxyhydroxide shells rich in high‐valent metal sites anchored on metallic NiCo nanowires. The optimized catalyst exhibits exceptional OER performance in 1 M KOH, requiring overpotentials of 191, 283, and 325 mV to achieve current densities of 10, 500, and 1000 mA cm −2 , respectively, with a low Tafel slope of 42.77 mV dec −1 . It demonstrates remarkable stability, sustaining 100 mA cm −2 for over 500 h with minimal potential decay (1.8%). Furthermore, a two‐electrode electrolyzer using A‐NiCoFe@NiCo/NF as the anode achieves a cell voltage of 1.50 V at 10 mA cm −2 , outperforming the Pt/C||RuO 2 benchmark. Density functional theory (DFT) calculations reveal that the amorphous shell with high‐valence metal sites significantly reduces the free energy barrier of the rate‐limiting O* formation step. This work highlights the potential of MOFs‐derived amorphous catalysts for industrial water splitting.