Trace nitrogen-incorporation stimulates dual active sites of nickel catalysts for efficient hydrogen oxidation electrocatalysis

• Trace nitrogen atoms are successfully inserted into the surface of Ni metal. • Trace nitrogen-incorporation can greatly activate monometallic Ni catalysts. • Apparent charge redistribution of Ni occurs at micro-heterogeneous interfaces. • It shifts the d-band center of Ni atoms for favorable adsorption kinetics. • The synergistic dual-active sites enhance HOR performance. The insufficient activity of Ni-based catalysts toward hydrogen oxidation reaction (HOR) severely hinders their deployment in alkaline polymer electrolyte fuel cells. Here, we demonstrate that trace nitrogen-incorporation can greatly activate monometallic Ni catalysts by constructing synergetic dual active sites across micro-heterogeneous interfaces, resulting in impressive HOR electrocatalytic performance that rivals that of state-of-the-art Pt/C catalysts in alkaline media. The obtained catalyst achieves a high specific activity of 0.074 mA cm −2 , a high mass activity of 60.9 A g −1 , and outperforms both Ni 3 N and Ni analogues, uncovering an unexpected nitrogen-incorporation criterion for Ni electrocatalysts. Moreover, it also exhibits a remarkable CO tolerance capacity that Pt/C lacks. Mechanistic studies reveal that self-regulated d-band centers of Ni (downshift) in Ni-N bonding and Ni (upshift) in Ni-Ni bonding derived from apparent charge redistribution can weaken hydrogen binding energy and increase hydroxyl binding energy simultaneously, resulting in the HOR enhancement.