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•CeO2 and nitrogen co-decoration are proposed to boost the OER activity of NiO.•The strong electron coupling among Ce/N-NiO can induce the rich Ni3+ surface.•The surface electron reconfiguration energetically promotes the adsorption of OH–.•Ce/N-NiO shows superior OER property with a low overpotential of 250 mV.•The OER activity of Ce/N-NiO outstrips RuO2 at high current density.
Nickel oxide (NiO) has emerged as a promising electrocatalyst for oxygen evolution reaction (OER) catalysis but undergoes insufficient active sites and unfavorable OH– adsorption properties. Herein, we develop an effective CeO2 and nitrogen co-decoration strategy to boost the OER performance of NiO (Ce/N-NiO) nanoparticles dramatically. The strong electron coupling among Ce/N-NiO nanoparticles provide exceptional facilities for the interface electron transfer from nitrogen-doped NiO to CeO2, and further induces the formation of rich Ni3+ surface, endowing it with abundant active sites. Besides, the surface electron reconfiguration energetically promotes the adsorption of OH–, resulting in fast reaction kinetics. As expected, the Ce/N-NiO sample shows superior OER property with a low overpotential of 250 mV at 10 mA cm−2. Particularly, when the current density exceeds 90 mA cm−2, the OER activity of Ce/N-NiO outstrips noble-metal-based RuO2. This co-decoration approach provides a practical guide for designing high-performance catalysts for OER and beyond.