Studies on the roles of vanadyl sulfate and sodium nitrite in catalytic oxidation of benzyl alcohol with molecular oxygen  

作　　者：Zhongtian Du Junxia Liu Tianliang Lu Yangyang Ma Jie Xu 

机构地区：[1]State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,Dalian National Laboratory for Clean Energy [2]University of Chinese Academy of Sciences

出　　处：《Science China Chemistry》2015年第1期114-122,共9页中国科学（化学英文版）

基　　金：financially supported by the National Natural Science Foundation of China(21203180,21233008)

摘　　要：An efficient catalytic system consisting of vanadyl sulfate/sodium nitrite was disclosed previously for the oxidation of benzylic alcohols into aldehydes with molecular oxygen.However,the roles of catalyst components were not investigated.In this paper,we examined catalytic oxidation of benzyl alcohol as a model reaction,especially by infrared spectroscopy.The role of each component is discussed including nitrite,vanadyl,sulphate,and water.Sodium nitrite could be converted into nitrate and nitric acid.The vanadium(IV)could be smoothly oxidized into vanadium(V)under mild and acidic conditions without any organic ligands.The transformation of sulfate and bisulfate,the cessation of an induction period,and the oxidation of benzyl alcohol were closely interrelated.The multiple roles of water are discussed,including reduction of the induction period,participation in redox cycles of nitric compounds,deactivation of vanadium,and as a byproduct of oxidation.This study contributes to further development of aerobic oxidation using vanadium based catalysts.An efficient catalytic system consisting of vanadyl sulfate/sodium nitrite was disclosed previously for the oxidation of benzylic alcohols into aldehydes with molecular oxygen. However, the roles of catalyst components were not investigated. In this paper, we examined catalytic oxidation of benzyl alcohol as a model reaction, especially by infrared spectroscopy. The role of each component is discussed including nitrite, vanadyl, sulphate, and water. Sodium nitrite could be converted into nitrate and nitric acid. The vanadium（IV） could be smoothly oxidized into vanadium（V） under mild and acidic conditions without any organic ligands. The transformation of sulfate and bisulfate, the cessation of an induction period, and the oxidation of benzyl alcohol were closely interrelated. The multiple roles of water are discussed, including reduction of the induction period, participation in redox cycles of nitric compounds, deactivation of vanadium, and as a byproduct of oxidation. This study contributes to further development of aerobic oxidation using vanadium based catalysts.

关 键 词：catalytic oxidation ALCOHOL infrared spectroscopy NITRITE VANADIUM 

分 类 号：O625.34[理学—有机化学]