ABSTRACT Electrocatalytic urea oxidation reaction (UOR) enables simultaneous wastewater purification and energy‐efficient hydrogen production, despite facing slow kinetics and competing oxygen evolution. Herein, a high‐performance Ce/Ni 2− x Mo x P catalyst was synthesized through Ce and Mo dual‐modulation to dynamically regulate Ni‐P phase transitions and construct atomic‐scale electron transfer networks. Investigations reveal that the Ce 3+ /Ce 4+ redox cycle triggers oxygen vacancy formation and steers the transition from stable Ni 3 P to metastable Ni 2 P, while Mo 6+ acts as an electron acceptor to optimize the electronic structure of Ni sites. Their synergistic interaction significantly lowers the phase transition barrier and boosts urea adsorption/activation. The catalyst achieves a current density of 100 mA cm ‒2 at a low potential of 1.32 V for UOR and demonstrates exceptional stability. Moreover, a urea electrolysis system constructed based on the optimized Ce/Ni 2− x Mo x P bifunctional catalyst reaches 400 mA cm ‒2 at just 1.68 V, significantly outperforming conventional water electrolysis, as well as maintaining operation for over 460 h at 500 mA cm ‒2 with a minimal decay rate of 0.11 mV h ‒1 . This work elucidates the atomic‐scale mechanism of Ce‐Mo cooperative regulation of electronic structure and phase transformation, providing a new strategy for designing efficient non‐noble‐metal electrocatalysts and advancing the industrialization of urea electrolysis.
Qiu et al. (Thu,) studied this question.