Abstract
Epoxidation of 2-cyclohexen-1-ol with TBHP and TiO2–SiO2, Fe2O3–SiO2 and SiO2 aerogels has been studied. The influence of surface silanol groups and transition metal impurities in titania–silica on the product distribution has been analyzed. The results, supported by literature data, indicate that high surface area silica cannot generally be regarded as an inert matrix in epoxidation catalysts. Contribution of Ti-free silica limits the selectivity of Ti- and Si-containing catalysts in demanding epoxidation reactions. The activity of silica – together with the background oxidation of the olefin – may lead to overestimated intrinsic activities when the reaction rate is related to the Ti content of the catalyst.
Similar content being viewed by others
References
M. Beller andC. Blom, Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals ( Wiley-VCH, Weinheim, 1998 ).
M. Dusi,C. Beck,T. Mallat andA. Baiker, in: Catalysis of Organic Reactions, ed. M.E. Ford ( Dekker, Allentown, 2000 ) p. 315.
A. Corma,A. Fuerte,M. Iglesias andF. Sànchez, J. Mol. Catal. A 107 (1996) 225.
D.C. Sherrington, in: Supported Reagents and Catalysts in Chemistry, eds. B.K. Hodnett,A.P. Kybett,J.H. Clark andK. Smith ( Royal Soc. Chem., Cambridge, 1998 ) p. 220.
T. Tatsumi,M. Yako,M. Nakamura,Y. Yuhara andH. Tominaga, J. Mol. Catal. 78 (1993) L41.
R. Kumar,G.C.G. Pais,B. Pandey andP. Kumar, J. Chem. Soc. Chem. Commun. (1995) 1315.
C. Cativiela,J.M. Fraile,J.I. Garcia andJ.A. Mayoral, J. Mol. Catal. A 112 (1996) 259.
R. Hutter,T. Mallat,A. Peterhans andA. Baiker, J. Catal. 172 (1997) 427.
M. Dusi,T. Mallat andA. Baiker, J. Mol. Catal. A 138 (1999) 15.
H. Kochkar andF. Figueras, J. Catal. 171 (1997) 420.
R. Hutter,T. Mallat,A. Peterhans andA. Baiker, J. Mol. Catal. A 138 (1999) 241.
M. Dusi,T. Mallat andA. Baiker, J. Catal. 187 (1999) 191.
J.L. Sotelo,R. Van Grieken andC. Martos, Chem. Commun. (1999) 549.
M.B. D'Amore andS. Schwarz, Chem. Commun. (1999) 121.
C.A. Müller,M. Maciejewski,T. Mallat andA. Baiker, J. Catal. 184 (1999) 280.
C.A. Müller,R. Deck,T. Mallat andA. Baiker, Topics Catal. 11/12 (2000) 369.
C.B. Khouw,C.B. Dartt,J.A. Labinger andM.E. Davis, J. Catal. 149 (1994) 195.
R. Hutter,T. Mallat andA. Baiker, J. Catal. 153 (1995) 177.
S. Klein,S. Thorimbert andW.F. Maier, J. Catal. 163 (1996) 476.
D.T. On,M.P. Kapoor andS. Kaliaguine, Chem. Commun. (1996) 1161.
K.B. Sharpless,C.H. Behrens,T. Katsuki,A.W.M. Lee,V.S. Martin,M. Takatani,S.M. Viti,F.J. Walker andS.S. Woodard, Pure Appl. Chem. 55 (1983) 589.
R. Antonioletti,F. Bonadies,L. Locati andA. Scettri, Tetrahedron Lett. 33 (1992) 3205.
L. Palombi,F. Bonadies andA. Scettri, Tetrahedron 53 (1997) 11376.
C.A. Müller,A. Gisler,M. Schneider,T. Mallat andA. Baiker, Catal. Lett. 64 (2000) 9.
R. Hutter,D. Dutoit,T. Mallat,M. Schneider andA. Baiker, J. Chem. Soc. Chem. Commun. (1995) 163.
J. Bu andH.K. Rhee, Catal. Lett. 65 (2000) 141.
H. Nur,S. Ikeda andB. Ohtani, Chem. Commun. (2000) 2235.
Z. Liu,G.M. Crumbaugh andR.J. Davis, J. Catal. 159 (1996) 83.
U. Arnold,R.S. da Cruz,D. Mandelli andU. Schuchardt, J. Mol. Catal. A 165 (2001) 149.
F. Launay andH. Patin, New J. Chem. 21 (1996) 247.
G. Rothenberg,L. Feldberg,H. Wiener andY. Sasson, J. Chem. Soc. Perkin Trans. II (1998) 2429.
M.L. Kremer, Phys. Chem. Chem. Phys. 1 (1999) 3595.
P.E. Sinclair andC.R.A. Catlow, J. Phys. Chem. B 103 (1999) 1084.
R.J. Davis andZ.F. Liu, Chem. Mater. 9 (1997) 2311.
F. Haber andJ. Weiss, Proc. R. Soc. London Ser. A 147 (1934) 332.
R.A. Sheldon andJ.A.V. Doorn, J. Catal. 31 (1973) 427.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Beck, C., Mallat, T. & Baiker, A. On the Limited Selectivity of Silica-Based Epoxidation Catalysts. Catalysis Letters 75, 131–136 (2001). https://doi.org/10.1023/A:1016700323552
Issue Date:
DOI: https://doi.org/10.1023/A:1016700323552