For the oxygen evolution reaction (OER), achieving precise electronic modulation of the active centers in metal (oxy)hydroxides (MOOH) remains a considerable challenge. Herein, we demonstrate that Ni doping effectively optimizes the electronic structure of Fe sites in FeOOH, leading to enhanced electrical conductivity and promoted charge transfer to oxygen-containing intermediates. This electronic modification strengthens the adsorption of reactants and significantly boosts the intrinsic OER activity of the Fe sites in Ni-FeOOH. Ni-doped FeOOH nanosheets are directly cover on Fe2O3 nanorods through a spontaneous metal corrosion strategy at room temperature. The unique hierarchical structure promotes the exposure of active sites and facilitates mass transfer. The optimized IF/Fe2O3@Ni-FeOOH-6 demonstrates exceptional OER performance, achieving an overpotential of 220 mV at 10 mA cm -2 and a Tafel slope of 26.6 mV dec -1 in alkaline media. Density functional theory simulations and electrochemical measurements indicate that the enhanced OER activity is due to Ni-doping, which effectively modulates the electronic structure of Fe sites, thereby lowering the reaction energy barrier for *OH → *O. This work provides a cost-effective and sustainable strategy for incorporating Ni into FeOOH and altering the local electronic structure of Fe sites.
