Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks

Carla Calabrese, Luca Fusaro, Leonarda Francesca Liotta, Francesco Giacalone, Adrien Comès, Vincenzo Campisciano, Carmela Aprile, Michelangelo Gruttadauria

Research output: Contribution to journalArticle

Abstract

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values, up to 5502 and 1081 respectively for glycidol conversion at 100 °C and up to 4942 and 1122 for epichlorohydrin conversion at 150 °C after 3 h, were obtained. Such outstanding productivity values were ascribed to the optimal organic/inorganic (i. e., imidazolium moiety/POSS support) weight ratio. The recyclability of the materials was successfully verified for five consecutive runs allowing their consideration as promising candidates for continuous flow technologies.

Original languageEnglish
Pages (from-to)1536-1543
Number of pages8
JournalChemPlusChem
Volume84
Issue number10
DOIs
Publication statusPublished - 1 Oct 2019

Fingerprint

glycidol
Carbonates
Carbon Dioxide
Nanostructures
Productivity
Epichlorohydrin
Catalysts
Hybrid materials
Iodides
Bromides
Nuclear magnetic resonance spectroscopy
Thermogravimetric analysis
Infrared spectroscopy
Metals
Chemical analysis

Keywords

  • carbon dioxide conversion
  • cyclic carbonates
  • heterogeneous catalysis
  • imidazolium salts
  • polyhedral oligomeric silsesquioxanes

Cite this

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title = "Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks",
abstract = "Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values, up to 5502 and 1081 respectively for glycidol conversion at 100 °C and up to 4942 and 1122 for epichlorohydrin conversion at 150 °C after 3 h, were obtained. Such outstanding productivity values were ascribed to the optimal organic/inorganic (i. e., imidazolium moiety/POSS support) weight ratio. The recyclability of the materials was successfully verified for five consecutive runs allowing their consideration as promising candidates for continuous flow technologies.",
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Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks. / Calabrese, Carla; Fusaro, Luca; Liotta, Leonarda Francesca; Giacalone, Francesco; Comès, Adrien; Campisciano, Vincenzo; Aprile, Carmela; Gruttadauria, Michelangelo.

In: ChemPlusChem, Vol. 84, No. 10, 01.10.2019, p. 1536-1543.

Research output: Contribution to journalArticle

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T1 - Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks

AU - Calabrese, Carla

AU - Fusaro, Luca

AU - Liotta, Leonarda Francesca

AU - Giacalone, Francesco

AU - Comès, Adrien

AU - Campisciano, Vincenzo

AU - Aprile, Carmela

AU - Gruttadauria, Michelangelo

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N2 - Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values, up to 5502 and 1081 respectively for glycidol conversion at 100 °C and up to 4942 and 1122 for epichlorohydrin conversion at 150 °C after 3 h, were obtained. Such outstanding productivity values were ascribed to the optimal organic/inorganic (i. e., imidazolium moiety/POSS support) weight ratio. The recyclability of the materials was successfully verified for five consecutive runs allowing their consideration as promising candidates for continuous flow technologies.

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