Solvothermal synthesis of VO₂ nanoparticles with locally patched V₂O₅ surface layer and their morphology-dependent catalytic properties for the oxidation of alcohols

Vanadium oxides are promising oxidation catalysts because of their rich redox chemistry. We report the synthesis of VO2 nanocrystals with VO2(B) crystal structure. By varying the mixing ratio of the components of a binary ethanol/water mixture, different VO2 nanocrystal morphologies (nanorods, -urchins, and -sheets) could be made selectively in pure form. Polydisperse VO2(B) nanorods with lengths between 150 nm and a few micrometers were formed at large water : ethanol ratios between 4 : 1 and 3 : 2. At a water : ethanol ratio of 1 : 9 VO2 nanosheets with diameters of similar to 50-70 nm were formed, which aggregated to nano-urchins with diameters of similar to 200 nm in pure ethanol. The catalytic activity of VO2 nanocrystals for the oxidation of alcohols was studied as a function of nanocrystal morphology. VO2 nanocrystals with all morphologies were catalytically active. The activity for the oxidation of benzyl alcohol to benzaldehyde was about 30% higher than that for the oxidation of furfuryl alcohol to furfural. This is due to the substrate structure. The oxidation activity of VO2 nanostructures decreases in the order of nanourchins > nanosheets > nanorods.