Photocatalytic Cyclohexanone Oxime Synthesis from Ambient Air and KA Oil

Photocatalysis offers a sustainable alternative for cyclohexanone oxime synthesis. However, multielectron and multiproton chemical transformations and synergic C-N coupling have posed tremendous barriers. To overcome these challenges, we intimately integrate quantum dot (QD) photocatalysts with a molecular iron-polypyridine complex and achieve photocatalytic cyclohexanone oxime formation for the first time. Mechanistic studies reveal that the close contact between CdS QDs and molecular iron-polypyridine complex boosts rapid photogenerated electron transfer to drive fast and continuous NO_x^- reduction. Simultaneously, photogenerated holes perform cyclohexanol oxidation to cyclohexanone coordinated to CdS QDs. More strikingly, the controllable formation and coordination with NH₂OH intermediate by the molecular complex enable synergic C-N coupling for cyclohexanone oxime synthesis with near-unity NO_x^- conversion and 82.5 ± 1.7% selectivity. Through tandem plasma-driven N₂ oxidation and photocatalysis, 0.395 g of cyclohexanone oxime is obtained from ambient air and ketone-alcohol (KA) oil, which offers a competitive candidate for cyclohexanone oxime synthesis and encourages value-added nitrogenous chemical transformation from abundant resource molecules.