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Non-hydrolytic synthesis of titanosilicate xerogels by acetamide elimination and their use as epoxidation catalysts

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Abstract

Novel non-hydrolytic syntheses of titanosilicate xerogels by polycondensation of silicon acetate, Si(OAc)4, with titanium (IV) dimethylamide or diethylamide, Ti(NR2)4 (R = Me, Et), are presented. The reactions are based on acetamide elimination and yield gels with a high content of Si–O−Ti bonds in comparison with the ester elimination route. Although a ligand exchange was observed, it was interestingly not followed by homo-condensation and during the synthesis the phase separation to SiO2 and TiO2 was avoided. The degree of condensation reached up to 68 %. The xerogels prepared for a comparison by ester elimination from Si(OAc)4 and titanium (IV) isopropoxide featured a significantly lower content of the Si–O–Ti bonds. The initial tests in the epoxidation of cyclohexene by cumyl hydroperoxide (CHP) indicated a high selectivity and moderate activity of the xerogels. The catalytic properties were significantly improved by combining non-hydrolytic and hydrolytic methods yielding mesoporous and homogeneous Si/Ti mixed oxides. The catalysts prepared by these methods provided a complete epoxidation of cyclohexene in 2 h at 65 °C.

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Acknowledgments

Authors thank the University of Cologne and the project CEITEC—Central European Institute of Technology (CZ.1.05/1.1.00/02.0068) for the financial assistance. The ERASMUS program is acknowledged for enabling the stay of A. S. in Cologne. Authors thank Dr. Z. Moravec for measuring N2 adsorption–desorption isotherms, L. Xiao, Dr. S. Stucky, Dr. V. Vavra, and Dr. P. Bezdicka for recording the XRD data, O. Arslan and Dr. Z. Moravec for measuring thermal analysis, and J. Abbott for assistance with the solid state NMR experiments. The helpful discussions with Dr. W. Tyrra, Dr. A. P. Singh and Dr. S. Stucky are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and CEITEC MU, Masaryk University, Brno, Czech Republic

    Ales Styskalik, David Skoda & Jiri Pinkas

  2. Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Cologne, Cologne, Germany

    Sanjay Mathur

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  1. Ales Styskalik
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  2. David Skoda
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  3. Jiri Pinkas
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Correspondence to Jiri Pinkas or Sanjay Mathur.

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Styskalik, A., Skoda, D., Pinkas, J. et al. Non-hydrolytic synthesis of titanosilicate xerogels by acetamide elimination and their use as epoxidation catalysts. J Sol-Gel Sci Technol 63, 463–472 (2012). https://doi.org/10.1007/s10971-012-2808-5

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