• • Achieved a Faradaic efficiency of 74.63% and a yield rate of 0.156 mmol h−1 cm−2 for cyclohexanone oxime (CHO) production via pulsed electrolysis on amorphous Bi2O3, outperforming potentiostatic conditions (55.43% FE on amorphous Bi) and offering a safer, cost-effective route compared to conventional hydroxylamine-based processes.
• • DFT calculations identified *NOH→*NHOH as the favored pathway on amorphous Bi2O3 (ΔG = 0.75 eV) versus *NOH→*N on amorphous Bi (ΔG = −1.76 eV), directly correlating with the higher FE for CHO and providing a mechanistic basis for catalyst design.
• • The kinetic barrier for *NH2OH→*NH2 is 0.86 eV, while *NH2OH desorption to NH2OH is barrierless, ensuring selective NH2OH release and subsequent coupling with cyclohexanone, a critical factor for industrial scalability.
• • The ICOHP analysis of the N–O bond in *NOH on amorphous Bi2O3 (1.34) versus amorphous Bi (0.84) indicates a weakened N–O bond (bond length 1.354 Å vs. 1.398 Å), which promotes the selective hydrogenation pathway and underscores the importance of the Bi2O3 phase in steering selectivity.