Direct conversion of N2 to nitrogen-containing organics via a plasma-electrochemical cascade reaction approaching 100% yield.

The direct electrosynthesis of nitrogen-containing organic chemicals from N2 is highly desirable for sustainable chemical manufacturing; however, its practical realization remains challenging due to the inherent inertness of N2. To overcome this limitation, a novel plasma-electrochemical cascade strategy is developed for the direct synthesis of cyclohexanone oxime (CHO) from N2 and cyclohexanone (CYC). The cascade strategy integrates the non-thermal plasma activation of N2 to generate nitrogen oxides (NOx) with the subsequent electrochemical reduction-coupling of NOx to organic precursors. A specially designed arc discharge plasma device equipped with circular electrodes achieves a high NOx concentration (957 mmol L-1), providing a concentrated reactive feed for downstream electrochemical conversion. To promote efficient CHO formation, a CuSA-MnC@TiO2 electrocatalyst is constructed to stabilize the *NH2OH intermediate formed during NOx reduction. Mechanistic studies confirmed NH2OH as the key coupling intermediate, with Cu sites preferentially adsorbing *NO2 and Mn sites adsorbing cyclohexanone. This synergistic effect enables excellent performance, achieving > 99% selectivity, a 99% CHO yield, and a production rate of 91.66 mmol g-1 h-1, which surpasses most previous N2-to-chemical conversion systems. Therefore, this cascade strategy provides an efficient and promising route for the direct utilization of N2 in the synthesis of valuable nitrogen-containing compounds.