Influence of surface modification of Ti-SBA15 catalysts on the epoxidation mechanism for cyclohexene with aqueous hydrogen peroxide
The thermolytic molecular precursor method was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support. The resulting surface Si-OH/Ti-OH sites of the Ti-SBA15 catalysts were modified with a series of (N,N-dimethylamino)trialkylsilanes, Me(2)N-SiMe(2)(R) (where...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 21(2005), 21 vom: 11. Okt., Seite 9576-83 |
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| Weitere Verfasser: | , , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2005
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article |
| Zusammenfassung: | The thermolytic molecular precursor method was used to introduce site-isolated Ti(IV) centers onto the surface of a mesoporous SBA15 support. The resulting surface Si-OH/Ti-OH sites of the Ti-SBA15 catalysts were modified with a series of (N,N-dimethylamino)trialkylsilanes, Me(2)N-SiMe(2)(R) (where R = Me, (n)Bu, or (n)Oc). Compared with the unmodified catalysts, the surface-modified catalysts are more active in the oxidation of cyclohexene with H(2)O(2) and exhibit a significantly higher selectivity (up to 58%) for cyclohexene oxide formation (vs allylic oxidation products). In situ Fourier transform infrared (FTIR) and diffuse reflectance UV visible (DRUV-vis) spectroscopies were used to probe this phenomenon, and it was determined that active sites with capped titanol centers, (SiO(surface))(3)Ti(OSiR(3)), likely undergo Ti-OOH formation upon addition of H(2)O(2) in a manner analogous to that for active sites of the type (SiO(surface))(3)TiOH. On the basis of the observation of similar Ti-OOH intermediates for both species, the electron-withdrawing effects on the Ti(IV) active site, resulting from the surface modification, are likely responsible for the observed increase in selectivity |
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| Beschreibung: | Date Completed 10.04.2007 Date Revised 06.10.2005 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |