Selective catalytic oxidative C−C bond cleavage with dioxygen is useful and challenging to prepare oxygenated fine chemicals. Herein we fabricated vanadium oxide–nitride composites as catalysts via a facile thermal treatment process, and the surface composition could be tuned by the thermal treatment temperature, which could affect catalytic oxidation of cyclohexanol significantly. By using such a V−N−C composite prepared at 500 °C, cyclohexanol could be selectively oxidized with dioxygen into lactones including δ‐valerolactone and γ‐butyrolactone, rather than common dicarboxylic acids. Cyclohexanone and 2‐cyclohexen‐1‐one were verified as two key intermediates. V3+ species in the form of vanadium nitride and vanadium (III) oxide were detected, and well dispersed on amorphous carbon with a low degree of graphitization. These findings will provide a reference for catalytic oxidative C−C bond cleavage with molecular oxygen under mild reaction conditions.

Selective oxidation of α-hydroxy esters is one of the most important methods to prepare high value-added α-keto esters. An efficient catalytic system consisting of Zn(NO3)2/VOC2O4 is reported for catalytic oxidation of α-hydroxy esters with molecular oxygen. Up to 99% conversion of methyl DL-mandelate or methyl lactate could be facilely obtained with high selectivity for its corresponding α-keto ester under mild reaction conditions. Zn(NO3)2 exhibited higher catalytic activity in combination with VOC2O4 compared with Fe(NO3)3 and different nitric oxidative gases were detected by situ attenuated total reflection infrared (ATR-IR) spectroscopy. UV-vis and ATR-IR results indicated that coordination complex formed in Zn(NO3)2 in CH3CN solution was quite different from Fe(NO3)3; it is proposed that the charge-transfer from Zn2+ to coordinated nitrate groups might account for the generation of different nitric oxidative gases. The XPS result indicate that nitric oxidative gas derived from the interaction of Zn(NO3)2 with VOC2O4 could be in favor of oxidizing VOC2O4 to generate active vanadium (V) species. It might account for different catalytic activity of Zn(NO3)2 or Fe(NO3)3 combined with VOC2O4. This work contributes to further development of efficient aerobic oxidation under mild reaction conditions.