Mo‐Mediated Phase Reconstruction in Ni‐Mo2C/Carbon Nanofibers for Enhanced Urea Electrolysis

Abstract Promoting the reconstruction of active phases is a pivotal strategy for enhancing electrocatalytic performance, yet it remains a formidable challenge in catalyst design and mechanistic understanding. Herein, a compelling strategy is reported to activate non‐noble Ni catalysts via electrochemical Mo‐mediated phase reconstruction in enhancing urea oxidation reaction (UOR) activity. The synergistic integration of Ni and high‐valence Mo species facilitates rapid electron transfer and induces the formation of catalytically active Ni‐based phases. In situ spectroscopic analyses reveal that Mo 2 C accelerates the generation of NiOOH as the key active phase, while both reaction kinetics for complete and incomplete oxidation pathways of UOR are enhanced. Density functional theory calculations unveil that electronic structure modulation, particularly the shift of the Ni d‐band center toward the Fermi level driven by Mo 2 C, lowers the adsorption energy of intermediates and reduces the energy barrier for UOR. The constructed Ni‐Mo 2 C/CNFs catalyst shows low potential, high current density, and good stability. The catalyst delivers efficient urea electrolysis with a cell voltage of only 1.42 V, which is 240 mV lower than that of conventional water electrolysis. This work offers some mechanistic insights for the rational design of next‐generation high‐performance electrocatalysts.