journal article·2012-09

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

Ales Styskalik, David Skoda, Jiri Pinkas, Sanjay Mathur

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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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Research context

OpenAlex topics: Mesoporous Materials and Catalysis · Polyoxometalates: Synthesis and Applications · Silicone and Siloxane Chemistry

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References (40)

Show source-provided references
1. Debecker DP, Mutin PH (2012) Non-hydrolytic sol–gel routes to heterogeneous catalysts. Chem Soc Rev 41:3624–365010.1039/c2cs15330k ↗
2. Vioux A (1997) Nonhydrolytic sol-gel routes to oxides. Chem Mater 9(11):2292–229910.1021/cm970322a ↗
3. Hay JN, Raval HM (2001) Synthesis of organic-inorganic hybrids via the non-hydrolytic sol-gel process. Chem Mater 13(10):3396–340310.1021/cm011024n ↗
4. Clavel G, Rauwel E, Willinger M-G, Pinna N (2009) Non-aqueous sol-gel routes applied to atomic layer deposition of oxides. J Mater Chem 19:454–46210.1039/B806215C ↗
5. Mutin PH, Vioux A (2009) Nonhydrolytic processing of oxide-based materials: simple routes to control homogeneity, morphology, and nanostructure. Chem Mater 21(4):582–59610.1021/cm802348c ↗
6. Niederberger M (2007) Nonaqueous sol-gel routes to metal oxide nanoparticles. Acc Chem Res 40(9):793–80010.1021/ar600035e ↗
7. Davis RJ, Liu Z (1997) Titania-silica: a model binary oxide catalyst system. Chem Mater 9(11):2311–232410.1021/cm970314u ↗
8. Fujiwara M, Wessel H, Hyung-Suh P, Roesky HW (2002) Formation of titanium tert-butylperoxo intermediate from cubic silicon-titanium complex with tert-butyl hydroperoxide and its reactivity for olefin epoxidation. Tetrahedron 58(2):239–24310.1016/S0040-4020(01)01144-9 ↗
9. Dusi M, Mallat T, Baiker A (2000) Epoxidation of functionalized olefins over solid catalysts. Catal Rev Sci Eng 42(1–2):213–27810.1081/CR-100100262 ↗
10. Lorret O, Lafond V, Mutin PH, Vioux A (2006) One-step synthesis of mesoporous hybrid titania-silica xerogels for the epoxidation of alkenes. Chem Mater 18(20):4707–470910.1021/cm061478q ↗
11. Müller CA, Deck R, Mallat T, Baiker A (2000) Hydrophobic titania-silica aerogels: epoxidation of cyclic compounds. Top Catal 11(1–4):369–37810.1023/A:1027202604286 ↗
12. Notari B, Willey RJ, Panizza M, Busca G (2006) Which sites are the active sites in TiO2-SiO2 mixed oxides? Catal Today 116(2):99–11010.1016/j.cattod.2006.02.086 ↗
13. Lafond V, Mutin PH, Vioux A (2002) Non-hydrolytic sol-gel routes based on alkylhalide elimination: toward better mixed oxide catalyst and new supports application to the preparation of a SiO2-TiO2 epoxidation catalyst. J Mol Catal A: Chem 182–183:81–8810.1016/S1381-1169(01)00487-3 ↗
14. Lafond V, Mutin PH, Vioux A (2004) Control of the texture of titania-silica mixed oxides prepared by nonhydrolytic sol-gel. Chem Mater 16(25):5380–538610.1021/cm0490569 ↗
15. Andrianainarivelo M, Corriu R, Leclerq D, Mutin PH, Vioux A (1996) Mixed oxides SiO2-ZrO2 and SiO2-TiO2 by a non-hydrolytic sol-gel route. J Mater Chem 6(10):1665–167110.1039/JM9960601665 ↗
16. Cojocariu AM, Mutin PH, Dumitriu E, Fajula F, Vioux A, Hulea V (2010) Mild oxidation of bulky organic compounds with hydrogen peroxide over mesoporous TiO2-SiO2 xerogels prepared by non-hydrolytic sol-gel. Appl Catal B 97:407–41310.1016/j.apcatb.2010.04.027 ↗
17. Cojocariu AM, Mutin PH, Dumitriu E, Aboulaich A, Vioux A, Fajula F, Hulea V (2010) Non-hydrolytic SiO2-TiO2 mesoporous xerogels-efficient catalysts for the mild oxidation of sulfur organic compounds with hydrogen peroxide. Catal Today 157:270–27410.1016/j.cattod.2010.02.046 ↗
18. Henderson GS, Fleet ME (1997) The structure of titanium silicate glasses investigated by Si K-edge X-ray absorption spectroscopy. J Non-Cryst Solids 211(3):214–22110.1016/S0022-3093(96)00640-0 ↗
19. Goubeau J, Mundiel RZ (1953) Uber das trichlorsiliciumacetat. Z Anorg Allg Chem 272(1–4):313–32610.1002/zaac.19532720511 ↗
20. Gueba-Neyroud T, Tumanskii B, Botoshansky M, Eisen MS (2007) Synthesis, characterization and catalytic activity of the complex titanium bis(dimethylmalonate)-bis(diethylamido) in the polymerization of propylene. J Organomet Chem 692(5):927–93910.1016/j.jorganchem.2006.10.031 ↗
21. Iwasaki M, Yasumori A, Shibata S, Yamane M (1994) Preparation of high homogeneity BaO-TiO2-SiO2 gel. J Sol-Gel Sci Technol 2:387–39110.1007/BF00486276 ↗
22. Jansen M, Guenther E (1995) Oxide gels and ceramics prepared by a nonhydrolytic sol-gel process. Chem Mater 7(11):2110–211410.1021/cm00059a019 ↗
23. Coltrain BK, Kelts LV, Armstrong NJ, Salva JM (1994) Silicon tetraacetate as a sol-gel precursor. J Sol-Gel Sci Technol 3:83–9010.1007/BF00486714 ↗
24. Innocenzi P (2003) Infrared spectroscopy of sol-gel derived silica-based films: a spectra-microstructure overview. J Non-Cryst Sol 316(2–3):309–31910.1016/S0022-3093(02)01637-X ↗
25. Deacon GB, Phillips RJ (1980) Relationship between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coord Chem Rev 33(3):227–25010.1016/S0010-8545(00)80455-5 ↗
26. Alcock NW, Tracy VM, Waddington TC (1976) Acetates and acetato-complexes. 2. Spectroscopic studies. J Chem Soc Dalton 21:2243–224610.1039/dt9760002243 ↗
27. Rotzinger FP, Kesselman-Truttmann JM, Hug SJ, Shklover V, Graetzel M (2004) Structure and vibrational spectrum of formate and acetate adsorbed from aqueous solution onto the TiO2 rutile (110) surface. J Phys Chem B 108(16):5004–501710.1021/jp0360974 ↗
28. Dutoit DCM, Schneider M, Baiker A (1995) Titania-silica mixed oxides. 1. Influence of sol-gel and drying conditions on structural properties. J Catal 153(1):165–17610.1006/jcat.1995.1118 ↗
29. Smith DY, Black CE, Homes CC, Shiles E (2007) Optical properties of TiO2-SiO2 glass over a wide spectral range. Phys Stat Sol 4(3):838–84210.1002/pssc.200673847 ↗
30. Frot T, Cochet S, Laurent G, Sassoye C, Popall M, Sanchez C, Rozes L (2010) Ti8O8(OOCR)16, a new family of titanium–oxo clusters: potential NBUs for reticular chemistry. Eur J Inorg Chem 36:5650–565910.1002/ejic.201000807 ↗
31. Birnie DP III, Bendzko NJ (1999) 1H and 13C NMR observation of the reaction of acetic acid with titanium isopropoxide. Mater Chem Phys 59:26–3510.1016/S0254-0584(99)00021-8 ↗
32. Balmer ML, Bunker BC, Wang LQ, Peden CHF, Su Y (1997) Solid-state 29Si MAS NMR study of titanosilicates. J Phys Chem B 101(45):9170–917910.1021/jp971429o ↗
33. Labouriau A, Higley TJ, Earl WL (1998) Chemical shift prediction in the 29Si MAS NMR of titanosilicates. J Phys Chem B 102(16):2897–290410.1021/jp9716703 ↗
34. Zibrowius B, Weidenthaler C, Schmidt W (2003) Sorbate-induced changes in the framework of the titanosilicate ETS-10 as detected by 29Si MAS NMR spectroscopy and X-ray powder diffraction. Phys Chem Chem Phys 5(4):773–77710.1039/b210235h ↗
35. Eimer GA, Casuscelli SG, Ghione GE, Crivello ME, Herrero ER (2006) Synthesis, characterization and selective oxidation properties of Ti-containing mesoporous catalysts. Appl Catal A General 298:32–24210.1016/j.apcata.2005.09.015 ↗
36. Liu Z, Davis RJ (1994) Investigation of the structure of microporous Ti-Si mixed oxides by X-ray, UV reflectance, FT-Raman, and FT-IR spectroscopies. J Phys Chem 98:1253–126110.1021/j100055a035 ↗
37. Murugavel R, Davis P, Shete VS (2003) Reactivity studies, structural characterization, and thermolysis of cubic titanosiloxanes: precursors to titanosilicate materials which catalyze olefin epoxidation. Inorg Chem 42(15):4696–470610.1021/ic034317m ↗
38. Mathur S, Veith M, Shen H, Hüfner S, Jilavi MH (2002) Structural and optical properties of NdAlO3 nanocrystals embedded in an Al2O3 matrix. Chem Mater 14(2):568–58210.1021/cm0111433 ↗
39. Coles MP, Lugmair CG, Terry KW, Tilley TD (2000) Titania-silica materials from the molecular precursor Ti[OSi(O t Bu)3]4: selective epoxidation catalysts. Chem Mater 12(1):122–13110.1021/cm990444y ↗
40. Hutter R, Mallat T, Baiker A (1995) Titania-silica mixed oxides. 2. Catalytic behavior in olefin epoxidation. J Catal 153(1):177–18910.1006/jcat.1995.1119 ↗