Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction

Hydroxylamine (HA, NH₂OH) is a critical feedstock in the production of various chemicals and materials, and its efficient and sustainable synthesis is of great importance. Electroreduction of nitrate on Cu-based catalysts has emerged as a promising approach for green ammonia (NH₃) production, but the electrosynthesis of HA remains challenging due to overreduction of HA to NH₃. Herein, we report the first work on ketone-mediated HA synthesis using nitrate in water. A metal-organic-framework-derived Cu catalyst was developed to catalyze the reaction. Cyclopentanone (CP) was used to capture HA in situ to form CP oxime (CP-O) with C═N bonds, which is prone to hydrolysis. HA could be released easily after electrolysis, and CP was regenerated. It was demonstrated that CP-O could be formed with an excellent Faradaic efficiency of 47.8%, a corresponding formation rate of 34.9 mg h^-1 cm^-2, and a remarkable carbon selectivity of >99.9%. The hydrolysis of CP-O to release HA and CP regeneration was also optimized, resulting in 96.1 mmol L^-1 of HA stabilized in the solution, which was significantly higher than direct nitrate reduction. Detailed in situ characterizations, control experiments, and theoretical calculations revealed the catalyst surface reconstruction and reaction mechanism, which showed that the coexistence of Cu⁰ and Cu⁺ facilitated the protonation and reduction of *NO₂ and *NH₂OH desorption, leading to the enhancement for HA production.