New Insights on the Oxidation of Unsaturated Fatty Acid Methyl Esters Catalyzed by Niobium(V) Oxide. A Study of the Catalyst Surface Reactivity

The catalytic properties of niobium(V) oxide (Nb2O5-CBMN) of different grades: amorphous, optical and ultra-pure, untreated or heat-treated at 400, 500, 700 and 900 ◦C were studied, before and after interaction with H2O2, by in situ Raman, FTIR-ATR and diffuse reflectance UV-Visible spectroscopy. The presence of different reaction sites for NbO7 and NbO8 type systems, which are directly related to surface defects present in different states of crystallization, were fully characterized. The reactivity of different catalysts obtained from niobium(V) oxide was investigated, using the oxidation of methyl linoleate in the presence of hydrogen peroxide as probe reaction. The reaction was followed by GC-MS, as well as by 1H and 13C NMR spectrometry and the dominant product was 9-oxo-nonanoic acid methyl ester. A reaction mechanism related to an auto-oxidation process must be occurring, leading initially to the formation of hydroperoxides, which decompose rapidly via Hock-type rearrangement, leading to the formation of aldehydes.