Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins
Titanosilicates (Ti-SiO<sub>2</sub>) are well-known catalysts for the epoxidation of olefins. Isolated Ti inserted in the silica framework in tetrahedral coordination are the active species. Recently, adjusting the hydrophobic/hydrophilic balance of such catalysts’ surfaces has appeared...
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MDPI AG
2021-02-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/11/2/196 |
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| author | Lucia E. Manangon-Perugachi Valentin Smeets Alvise Vivian Itika Kainthla Pierre Eloy Carmela Aprile Damien P. Debecker Eric M. Gaigneaux |
| author_facet | Lucia E. Manangon-Perugachi Valentin Smeets Alvise Vivian Itika Kainthla Pierre Eloy Carmela Aprile Damien P. Debecker Eric M. Gaigneaux |
| author_sort | Lucia E. Manangon-Perugachi |
| collection | DOAJ |
| description | Titanosilicates (Ti-SiO<sub>2</sub>) are well-known catalysts for the epoxidation of olefins. Isolated Ti inserted in the silica framework in tetrahedral coordination are the active species. Recently, adjusting the hydrophobic/hydrophilic balance of such catalysts’ surfaces has appeared as a promising tool to further boost their performance. However, adjusting the hydrophobic/hydrophilic balance via a one-pot classical sol-gel generally leads to a decrease in the Ti dispersion and/or collapse of the pore network. To overcome this limitation, hydrophobic mesoporous Ti-SiO<sub>2</sub> were here synthesized by aerosol-assisted one-pot sol–gel, which allowed the simultaneous control of their Ti loading, degree of methyl-functionalization, and textural properties. Methyl-functionalization was achieved by a partial substitution of tetraethoxy silane (TEOS) by methyltriethoxy silane (MTES) in different ratios. Solid-state <sup>29</sup>Si-NMR, FTIR, TGA, and vapor-phase water adsorption showed that methyl moieties were effectively incorporated, conferring a hydrophobic property to the Ti-SiO<sub>2</sub> catalysts. ICP-AES, DRUV, XPS, and N<sub>2</sub> physisorption demonstrated that Ti dispersion and textural properties were both successfully preserved upon the incorporation of the methyl moieties. In the epoxidation of cyclooctene with tert-butyl hydroperoxide as oxidant, the hydrophobic Ti-SiO<sub>2</sub> showed higher catalytic performance than pristine Ti-SiO<sub>2</sub> prepared without MTES. In addition to disentangling the positive effect of adjusting the hydrophobic/hydrophilic balance of epoxidation catalysts on their performance, this contribution highlights the advantages of the aerosol procedure to synthesize mesoporous functionalized catalysts with very high dispersion of active sites. |
| first_indexed | 2024-03-09T06:02:01Z |
| format | Article |
| id | doaj.art-26b905b8ec524341a51788c5ee90d3a3 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-09T06:02:01Z |
| publishDate | 2021-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-26b905b8ec524341a51788c5ee90d3a32023-12-03T12:07:25ZengMDPI AGCatalysts2073-43442021-02-0111219610.3390/catal11020196Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of OlefinsLucia E. Manangon-Perugachi0Valentin Smeets1Alvise Vivian2Itika Kainthla3Pierre Eloy4Carmela Aprile5Damien P. Debecker6Eric M. Gaigneaux7Institute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumUnit of Nanomaterial Chemistry, Department of Chemistry, University of Namur, 5000 Namur, BelgiumInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumUnit of Nanomaterial Chemistry, Department of Chemistry, University of Namur, 5000 Namur, BelgiumInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumInstitute of Condensed Matter and Nanosciences (IMCN), Université Catholique de Louvain (UCLouvain), Place Louis Pasteur 1, L4.01.09, 1348 Louvain-la-Neuve, BelgiumTitanosilicates (Ti-SiO<sub>2</sub>) are well-known catalysts for the epoxidation of olefins. Isolated Ti inserted in the silica framework in tetrahedral coordination are the active species. Recently, adjusting the hydrophobic/hydrophilic balance of such catalysts’ surfaces has appeared as a promising tool to further boost their performance. However, adjusting the hydrophobic/hydrophilic balance via a one-pot classical sol-gel generally leads to a decrease in the Ti dispersion and/or collapse of the pore network. To overcome this limitation, hydrophobic mesoporous Ti-SiO<sub>2</sub> were here synthesized by aerosol-assisted one-pot sol–gel, which allowed the simultaneous control of their Ti loading, degree of methyl-functionalization, and textural properties. Methyl-functionalization was achieved by a partial substitution of tetraethoxy silane (TEOS) by methyltriethoxy silane (MTES) in different ratios. Solid-state <sup>29</sup>Si-NMR, FTIR, TGA, and vapor-phase water adsorption showed that methyl moieties were effectively incorporated, conferring a hydrophobic property to the Ti-SiO<sub>2</sub> catalysts. ICP-AES, DRUV, XPS, and N<sub>2</sub> physisorption demonstrated that Ti dispersion and textural properties were both successfully preserved upon the incorporation of the methyl moieties. In the epoxidation of cyclooctene with tert-butyl hydroperoxide as oxidant, the hydrophobic Ti-SiO<sub>2</sub> showed higher catalytic performance than pristine Ti-SiO<sub>2</sub> prepared without MTES. In addition to disentangling the positive effect of adjusting the hydrophobic/hydrophilic balance of epoxidation catalysts on their performance, this contribution highlights the advantages of the aerosol procedure to synthesize mesoporous functionalized catalysts with very high dispersion of active sites.https://www.mdpi.com/2073-4344/11/2/196mesoporous titanosilicate TiO<sub>2</sub>-SiO<sub>2</sub>aerosol-assisted sol-gelone-pot methyl-functionalizationsurface hydrophobicityolefin epoxidation |
| spellingShingle | Lucia E. Manangon-Perugachi Valentin Smeets Alvise Vivian Itika Kainthla Pierre Eloy Carmela Aprile Damien P. Debecker Eric M. Gaigneaux Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins Catalysts mesoporous titanosilicate TiO<sub>2</sub>-SiO<sub>2</sub> aerosol-assisted sol-gel one-pot methyl-functionalization surface hydrophobicity olefin epoxidation |
| title | Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins |
| title_full | Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins |
| title_fullStr | Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins |
| title_full_unstemmed | Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins |
| title_short | Mesoporous Methyl-Functionalized Titanosilicate Produced by Aerosol Process for the Catalytic Epoxidation of Olefins |
| title_sort | mesoporous methyl functionalized titanosilicate produced by aerosol process for the catalytic epoxidation of olefins |
| topic | mesoporous titanosilicate TiO<sub>2</sub>-SiO<sub>2</sub> aerosol-assisted sol-gel one-pot methyl-functionalization surface hydrophobicity olefin epoxidation |
| url | https://www.mdpi.com/2073-4344/11/2/196 |
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