High-valent Zirconium-doping modified Co3O4 weave-like nanoarray boosts oxygen evolution reaction

• Zr-doping Co 3 O 4 electrocatalysts were fabricated on nickel foam. • Zr-doping Co 3 O 4 weave-like nanoarray exhibits excellent alkaline OER activity. • The free energy of potential rate-determining step is reduced. • Morphology and electronic structure of Co 3 O 4 were optimized by Zr doping. • The design of the experiment can be guided and predicted via DFT calculations. Zr-doping Co 3 O 4 weave-like nanoarray as an efficient OER catalyst was designed under the guidance of DFT calculations. Zr doping in Co 3 O 4 can accelerate potential rate-determining step, regulate electronic structure and morphology, therefore, boost OER activity. It is urgently crucial to design high-performance and low-cost electrocatalysis for oxygen evolution reaction (OER) toward associated renewable energy systems. Herein, we reported that a certain amount of Zirconium doping in Co 3 O 4 can regulate the electronic structure and morphology, therefore, boost the OER electrocatalytic performance. Zr doped Co 3 O 4 demonstrates more excellent OER activity than pure Co 3 O 4 , as confirmed by density functional theory (DFT) calculations and experimental results, where the acceleration of potential rate-determining step and the improvement of conductivity are attributed to the introduction of Zr-dopants. Specifically, the as-synthesized 3D Zr-Co 3 O 4 /NF exhibits prominent OER activity with low overpotential 307 mV to drive current density of 20 mA cm −2 , modest Tafel slope of 99 mV dec −1 and robust stability in 1 M KOH electrolyte. Our work reveals a novel approach to disclose Zr as a feasible dopant to optimize electronic structure and OER catalytic performance of metal oxides, and also proves the guiding role of DFT calculations for reasonable preparation of high-efficiency OER catalysts.