Synergistic Atomic Environment Optimization of Nickel–Iron Dual Sites by Co Doping and Cr Vacancy for Electrocatalytic Oxygen Evolution

The dual-site synergistic catalytic mechanism on NiFeOOH suggests weak adsorption of Ni sites and strong adsorption of Fe sites limited its activity toward alkaline oxygen evolution reaction (OER). Large-scale density functional theory (DFT) calculations confirm that Co doping can increase Ni adsorption, while the metal vacancy can reduce Fe adsorption. The combined two factors can further modulate the atomic environment and optimize the free energy toward oxygen-containing intermediates, thus enhancing the OER activity. Accordingly, we used Co doping and Cr vacancies to fabricate an amorphous catalyst of VCr,Co-NiFeOOH. It provides an OER overpotential of 239 mV at 100 mA cm–2 and high stability over 500 h at 500 mA cm–2 with a ∼98% potential retention. The resulting water electrolyzer based on an anion exchange membrane (AEM) exhibits a remarkable performance of 1 A cm–2 at 1.68 V in 1 M KOH. XPS, soft-XAS, and XANES combined with Bader charge analysis results reveal that the regulation of the local microenvironment can increase the valence state of Ni by Co doping, thus improving the adsorption energy on Ni sites. The Cr vacancy can alleviate the strong adsorption on Fe sites. DFT calculations confirm that the synergistic effect of Co doping and Cr vacancies can redistribute the charge on the Ni/Fe sites, optimize the d-band center of Ni and Fe, and endow the catalyst with Ni–Fe dual sites to reduce the energy barrier of the OER rate-determining step.