Well-defined Ni3N nanoparticles armored in hollow carbon nanotube shell for high-efficiency bifunctional hydrogen electrocatalysis

Alkaline H2-O2 fuel cells and water electrolysis are crucial for hydrogen energy recycling. However, the sluggish kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) in an alkaline medium pose significant obstacles. Thus, it is imperative but challenging to develop highly efficient and stable non-precious metal electrocatalysts for alkaline HOR and HER. Here, we present the intriguing synthesis of well-defined Ni3N nanoparticles armored within an N-doped hollow carbon nanotube shell (Ni3N@NC) via the conversion of a hydrogen-bonded organic framework (HOF) to metal-organic framework (MOF), followed by high-temperature pyrolysis. As-developed Ni3N@NC demonstrates exceptional bifunctionality in alkaline HOR/HER electrocatalysis, with a high HOR limiting current density of 2.67 mA cm-2 comparable to the benchmark 20 wt% Pt/C, while achieving a lead in overpotential of 145 mV and stronger CO-tolerance. Additionally, it achieves a low overpotential of 21 mV to attain a HER current density of 10 mA cm-2 with long-term stability up to 340 h, both exceeding those of Pt/C. Structural analyses and electrochemical studies reveal that the remarkable bifunctional hydrogen electrocatalytic performance of Ni3N@NC can be ascribed to the synergistic coupling among the well-dispersed small-sized Ni3N nanoparticles, chain-mail structure, and optimized electronic structure enabled by strong metal-support interaction. Furthermore, theoretical calculations indicate that the high-efficiency HOR/HER observed in Ni3N@NC is attributed to the strong OH- affinity, moderate H adsorption, and enhanced water formation/dissociation ability of the Ni3N active sites. This work underscores the significance of rational structural design in enhancing performance and inspires further development of advanced nanostructures for efficient hydrogen electrocatalysis.