Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides
Functionalized aluminosilicate materials were studied as catalysts for the conversion of different cyclic carbonates to the corresponding epoxides by the addition of CO<sub>2</sub>. Aluminum was incorporated in the mesostructured SBA-15 silica network. Thereafter, functionalization with...
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/24/8883 |
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| author | Luciano Atzori Adrien Comès Luca Fusaro Carmela Aprile Maria Giorgia Cutrufello |
| author_facet | Luciano Atzori Adrien Comès Luca Fusaro Carmela Aprile Maria Giorgia Cutrufello |
| author_sort | Luciano Atzori |
| collection | DOAJ |
| description | Functionalized aluminosilicate materials were studied as catalysts for the conversion of different cyclic carbonates to the corresponding epoxides by the addition of CO<sub>2</sub>. Aluminum was incorporated in the mesostructured SBA-15 silica network. Thereafter, functionalization with imidazolium chloride or magnesium oxide was performed on the Al_SBA-15 supports. The isomorphic substitution of Si with Al and the resulting acidity of the supports were investigated via <sup>27</sup>Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and NH<sub>3</sub> adsorption microcalorimetry. The Al content and the amount of MgO were quantified via inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. The anchoring of the imidazolium salt was assessed by <sup>29</sup>Si and <sup>13</sup>C MAS NMR spectroscopy and quantified by combustion chemical analysis. Textural and structural properties of supports and catalysts were studied by N<sub>2</sub> physisorption and X-ray diffraction (XRD). The functionalized systems were then tested as catalysts for the conversion of CO<sub>2</sub> and epoxides to cyclic carbonates in a batch reactor at 100 or 125 °C, with an initial CO<sub>2</sub> pressure (at room temperature) of 25 bar. Whereas the activity of the MgO/<i>x</i>Al_SBA-15 systems was moderate for the conversion of glycidol to the corresponding cyclic carbonate, the Al_SBA-15-supported imidazolium chloride catalysts gave excellent results over different epoxides (conversion of glycidol, epichlorohydrin, and styrene oxide up to 89%, 78%, and 18%, respectively). Reusability tests were also performed. Even when some deactivation from one run to the other was observed, a comparison with the literature showed the Al-containing imidazolium systems to be promising catalysts. The fully heterogeneous nature of the present catalysts, where the inorganic support on which the imidazolium species are immobilized also contains the Lewis acid sites, gives them a further advantage with respect to most of the catalytic systems reported in the literature so far. |
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| id | doaj.art-71a941dcf81e4238af0ebec4f9c3c048 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T16:02:17Z |
| publishDate | 2022-12-01 |
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| spelling | doaj.art-71a941dcf81e4238af0ebec4f9c3c0482023-11-24T16:59:05ZengMDPI AGMolecules1420-30492022-12-012724888310.3390/molecules27248883Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding EpoxidesLuciano Atzori0Adrien Comès1Luca Fusaro2Carmela Aprile3Maria Giorgia Cutrufello4Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, 09042 Monserrato, ItalyUnit of Nanomaterial Chemistry, Department of Chemistry, University of Namur, 5000 Namur, BelgiumUnit of Nanomaterial Chemistry, Department of Chemistry, University of Namur, 5000 Namur, BelgiumUnit of Nanomaterial Chemistry, Department of Chemistry, University of Namur, 5000 Namur, BelgiumDipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, 09042 Monserrato, ItalyFunctionalized aluminosilicate materials were studied as catalysts for the conversion of different cyclic carbonates to the corresponding epoxides by the addition of CO<sub>2</sub>. Aluminum was incorporated in the mesostructured SBA-15 silica network. Thereafter, functionalization with imidazolium chloride or magnesium oxide was performed on the Al_SBA-15 supports. The isomorphic substitution of Si with Al and the resulting acidity of the supports were investigated via <sup>27</sup>Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and NH<sub>3</sub> adsorption microcalorimetry. The Al content and the amount of MgO were quantified via inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. The anchoring of the imidazolium salt was assessed by <sup>29</sup>Si and <sup>13</sup>C MAS NMR spectroscopy and quantified by combustion chemical analysis. Textural and structural properties of supports and catalysts were studied by N<sub>2</sub> physisorption and X-ray diffraction (XRD). The functionalized systems were then tested as catalysts for the conversion of CO<sub>2</sub> and epoxides to cyclic carbonates in a batch reactor at 100 or 125 °C, with an initial CO<sub>2</sub> pressure (at room temperature) of 25 bar. Whereas the activity of the MgO/<i>x</i>Al_SBA-15 systems was moderate for the conversion of glycidol to the corresponding cyclic carbonate, the Al_SBA-15-supported imidazolium chloride catalysts gave excellent results over different epoxides (conversion of glycidol, epichlorohydrin, and styrene oxide up to 89%, 78%, and 18%, respectively). Reusability tests were also performed. Even when some deactivation from one run to the other was observed, a comparison with the literature showed the Al-containing imidazolium systems to be promising catalysts. The fully heterogeneous nature of the present catalysts, where the inorganic support on which the imidazolium species are immobilized also contains the Lewis acid sites, gives them a further advantage with respect to most of the catalytic systems reported in the literature so far.https://www.mdpi.com/1420-3049/27/24/8883cyclic carbonates synthesisCO<sub>2</sub> conversionsupported catalystsAl_SBA-15imidazolium chloride |
| spellingShingle | Luciano Atzori Adrien Comès Luca Fusaro Carmela Aprile Maria Giorgia Cutrufello Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides Molecules cyclic carbonates synthesis CO<sub>2</sub> conversion supported catalysts Al_SBA-15 imidazolium chloride |
| title | Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides |
| title_full | Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides |
| title_fullStr | Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides |
| title_full_unstemmed | Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides |
| title_short | Aluminosilicate-Supported Catalysts for the Synthesis of Cyclic Carbonates by Reaction of CO<sub>2</sub> with the Corresponding Epoxides |
| title_sort | aluminosilicate supported catalysts for the synthesis of cyclic carbonates by reaction of co sub 2 sub with the corresponding epoxides |
| topic | cyclic carbonates synthesis CO<sub>2</sub> conversion supported catalysts Al_SBA-15 imidazolium chloride |
| url | https://www.mdpi.com/1420-3049/27/24/8883 |
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