Formation of pyridine N-oxides using mesoporous titanium silicalite-1
Mesoporous titanium silicalite-1 (TS-1) prepared by carbon-templating is significantly more active than conventional TS-1 for the oxidation of pyridine derivatives using aqueous hydrogen peroxide as oxidant. The catalytic activity is increased by the system of mesopores that helps to overcome the configurational diffusion limitations within the microporous catalyst. The use of a carbon-template for generation of secondary porosity is more effective than desilication. The desilicated catalyst is slightly more active than conventional TS-1, probably due to a decrease of the mean diffusion path length. In contrast, carbon-templated mesopores provides an efficient transport throughout the zeolite, thus preventing deactivation due to product confinement. All catalysts were characterised by X-ray powder diffraction, scanning electron microscopy, UV–Vis spectroscopy and nitrogen physisorption. The results indicate that desilication may cause a surface densification of less catalytically active extra-framework Ti species. Carbon-templating is thus a more gentle and effective method for generating secondary porosity. Utilization of carbon-templated mesoporous TS-1 for oxidation of pyridine derivatives represents a new and environmentally friendly method to synthesise N-oxides.
KeywordsMesoporous TS-1 N-oxides Catalytic oxidation Carbon templating Desilication
We gratefully acknowledge the support of the Danish Council for Independent Research, Grant No. 10-093717 and Grant No. 12-127580. We would also like to thank for support from the Spanish Ministry of Science and Innovation (project CTQ2011-25517), and Unidad de Apoyo from Catalysis Institute (ICP-CSIC).
- 2.M. Padovan, F. Genoni, G. Leofanti, G. Petrini, P. Roffia, A. Cesana, US Patent 4.968.842, (1990)Google Scholar
- 3.M. Taramasso, G. Perego, B. Notari, US Patent 4.410.501, (1983)Google Scholar
- 4.G. Bellussi, A. Carati, M. G. Clerici, A. Esposito, R. Millini, F. Buonomo, BE Patent 1.001.038, (1989)Google Scholar
- 10.C. Madsen, C.J.H. Jacobsen, Chem. Commun. 673–674 (1999)Google Scholar