Photocatalytic Cyclohexanone Oxime Synthesis from Ambient Air and KA Oil
Shu‐Lin Meng, Chen Zhang, Jiahao Li, Chen‐Ho Tung, Li‐Zhu Wu
Abstract
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 NH 2 OH 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 N 2 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.