Selective Conversion NOx Into Isoxazoles via Co–Zn Electrocatalyst Steering the Reaction Pathway

ABSTRACT The electrocatalytic upcycling of NOx species into valuable N ‐heterocycles presents an attractive route, but it is challenged by complex paths and low catalytic activity. This work reports a highly selective strategy for the electrochemical reduction of NOx to isoxazoles via coupling with 1,3‐dicarbonyls, enabled by a Co–Zn dual‐atom catalyst (Co–Zn–NC). Interestingly, the system achieves a remarkable Faraday efficiency of 92% for isoxazole and significantly inhibits hydrogen and ammonia production. The unique electronic structure significantly regulates the energy barrier of nitrate reduction reaction and the hydrogen adsorption energy revealed by density functional theory calculations, while obtaining moderate affinity towards hydroxylamine intermediate and isoxazole product illustrated from the adsorption measurements. This strategy demonstrates exceptional universality across various nitrogen sources (NO 3 − , NO 2 − , NO, NO 2 ), carbon sources (1,3‐dicarbonyls), and a series of M–Zn–NC catalysts, establishing a novel paradigm for synthesizing structurally complex N─O heterocycles directly from inorganic nitrogen wastes and creating a new platform for sustainable molecular manufacturing.