Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2

Carla Calabrese, Leonarda F. Liotta, Francesco Giacalone, Michelangelo Gruttadauria, Carmela Aprile

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic species with Lewis or Brønsted acid functionalities which still represents a challenging aspect for the outcome of the process. The recyclability of the catalysts was successfully verified for four consecutive runs. The catalytic versatility was proved with a wide range of epoxides and with the most challenging oxetane on large scale (105–210 mmol) showing higher performances in comparison with other unmodified imidazolium-based catalytic systems. The new hybrids based on supported POSS nanostructures allowed the sustainable conversion of carbon dioxide under solvents- and metal-free reaction conditions with a full selectivity toward cyclic carbonates.

langue originaleAnglais
Pages (de - à)560-567
Nombre de pages8
journalChemCatChem
Volume11
Numéro de publication1
Les DOIs
étatPublié - 9 janv. 2019

Empreinte digitale

Carbonates
Hybrid materials
carbonates
Functional materials
epoxy compounds
Epoxy Compounds
versatility
productivity
Carbon Dioxide
Silicon Dioxide
carbon dioxide
Nanostructures
Carbon dioxide
selectivity
Productivity
Metals
Silica
silicon dioxide
catalysts
acids

Citer ceci

Calabrese, Carla ; Liotta, Leonarda F. ; Giacalone, Francesco ; Gruttadauria, Michelangelo ; Aprile, Carmela. / Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2. Dans: ChemCatChem. 2019 ; Vol 11, Numéro 1. p. 560-567.
@article{e4b47b7ef96c40b0bc17bc2cba00a116,
title = "Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2",
abstract = "Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic species with Lewis or Br{\o}nsted acid functionalities which still represents a challenging aspect for the outcome of the process. The recyclability of the catalysts was successfully verified for four consecutive runs. The catalytic versatility was proved with a wide range of epoxides and with the most challenging oxetane on large scale (105–210 mmol) showing higher performances in comparison with other unmodified imidazolium-based catalytic systems. The new hybrids based on supported POSS nanostructures allowed the sustainable conversion of carbon dioxide under solvents- and metal-free reaction conditions with a full selectivity toward cyclic carbonates.",
keywords = "CO2 conversion, cyclic carbonates, heterogeneous catalysis, imidazolium catalyst, POSS",
author = "Carla Calabrese and Liotta, {Leonarda F.} and Francesco Giacalone and Michelangelo Gruttadauria and Carmela Aprile",
year = "2019",
month = "1",
day = "9",
doi = "10.1002/cctc.201801351",
language = "English",
volume = "11",
pages = "560--567",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",
number = "1",

}

Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2. / Calabrese, Carla; Liotta, Leonarda F.; Giacalone, Francesco; Gruttadauria, Michelangelo; Aprile, Carmela.

Dans: ChemCatChem, Vol 11, Numéro 1, 09.01.2019, p. 560-567.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2

AU - Calabrese, Carla

AU - Liotta, Leonarda F.

AU - Giacalone, Francesco

AU - Gruttadauria, Michelangelo

AU - Aprile, Carmela

PY - 2019/1/9

Y1 - 2019/1/9

N2 - Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic species with Lewis or Brønsted acid functionalities which still represents a challenging aspect for the outcome of the process. The recyclability of the catalysts was successfully verified for four consecutive runs. The catalytic versatility was proved with a wide range of epoxides and with the most challenging oxetane on large scale (105–210 mmol) showing higher performances in comparison with other unmodified imidazolium-based catalytic systems. The new hybrids based on supported POSS nanostructures allowed the sustainable conversion of carbon dioxide under solvents- and metal-free reaction conditions with a full selectivity toward cyclic carbonates.

AB - Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic species with Lewis or Brønsted acid functionalities which still represents a challenging aspect for the outcome of the process. The recyclability of the catalysts was successfully verified for four consecutive runs. The catalytic versatility was proved with a wide range of epoxides and with the most challenging oxetane on large scale (105–210 mmol) showing higher performances in comparison with other unmodified imidazolium-based catalytic systems. The new hybrids based on supported POSS nanostructures allowed the sustainable conversion of carbon dioxide under solvents- and metal-free reaction conditions with a full selectivity toward cyclic carbonates.

KW - CO2 conversion

KW - cyclic carbonates

KW - heterogeneous catalysis

KW - imidazolium catalyst

KW - POSS

UR - http://www.scopus.com/inward/record.url?scp=85055932319&partnerID=8YFLogxK

U2 - 10.1002/cctc.201801351

DO - 10.1002/cctc.201801351

M3 - Article

AN - SCOPUS:85055932319

VL - 11

SP - 560

EP - 567

JO - ChemCatChem

JF - ChemCatChem

SN - 1867-3880

IS - 1

ER -