TY - JOUR
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
N1 - Funding Information:
We gratefully acknowledge the University of Palermo and the University of Namur. C.C. gratefully acknowledges the University of Palermo and University of Namur for a co‐funded PhD fellowship. This research used resources of the nuclear magnetic resonance service located at the University of Namur. This service is a member of the “Plateforme Technologique Physico‐Chemical Characterization” – PC 2 .
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/10/1
Y1 - 2019/10/1
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.
AB - 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.
KW - carbon dioxide conversion
KW - cyclic carbonates
KW - heterogeneous catalysis
KW - imidazolium salts
KW - polyhedral oligomeric silsesquioxanes
UR - http://www.scopus.com/inward/record.url?scp=85071873420&partnerID=8YFLogxK
U2 - 10.1002/cplu.201900408
DO - 10.1002/cplu.201900408
M3 - Article
AN - SCOPUS:85071873420
SN - 2192-6506
VL - 84
SP - 1536
EP - 1543
JO - ChemPlusChem
JF - ChemPlusChem
IS - 10
ER -