Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst

Acetalization of glycerol with various aldehydes has been carried out using mesoporous MoO3/SiO2 as a solid acid catalyst. A series of MoO3/SiO2 catalysts with varying MoO3 loadings (1–20 mol%) were prepared by sol–gel technique using ethyl silicate-40 and ammonium heptamolybdate as silica and molybdenum source respectively. The sol–gel derived samples were calcined at 500 °C and characterized using various physicochemical characterization techniques. The XRD of the calcined samples showed the formation of amorphous phase up to 10 mol% MoO3 loading and at higher loading of crystalline α-MoO3 on amorphous silica support. TEM analyses of the materials showed the uniform distribution of MoO3 nanoparticles on amorphous silica support. Raman spectroscopy showed the formation of silicomolybdic acid at low Mo loading and a mixture of α-MoO3 and polymolybdate species at high Mo loadings. Moreover the Raman spectra of intermediate loading samples also suggest the presence of β-MoO3. Acetalization of glycerol with benzaldehyde was carried out using series of MoO3/SiO2 catalysts with varying MoO3 loadings (1–20 mol%). Among the series, MoO3/SiO2 with 20 mol% MoO3 loadings was found to be the most active catalyst in acetalization under mild conditions. Maximum conversion of benzaldehyde (72%) was obtained in 8 h at 100 °C with 60% selectivity for the six-membered acetal using 20% MoO3/SiO2. Interestingly with substituted benzaldehydes under same reaction conditions the conversion of aldehydes decreased with increase in selectivity for six-membered acetals. These results indicate the potential of this catalyst for the acetalization of glycerol for an environmentally benign process.

Graphical abstractMoO3/SiO2 catalysts prepared by sol–gel synthesis using ethyl silicate-40 was used for acetalization of glycerol with various aldehydes. Structural characterization showed the formation of molybdenum oxide nanoparticles of 1–2 nm on mesoporous silica support with very high acidity. Raman spectroscopy confirmed the presence of silicomolybdic acid, β-MoO3, polymolybdate and α-MoO3 species with varying molybdenum content.Figure optionsDownload full-size imageDownload as PowerPoint slide