Highly cross-linked materials containing an imidazolium salt and magnesium porphyrin, either in the absence (TSP-Mg-imi) or in the presence (7a and 7b) of multi-walled carbon nanotubes (MWCNTs), were synthesized and used as heterogeneous bifunctional catalysts for the conversion of CO2 into cyclic carbonates. The metalloporphyrin moiety acts both as a “covalent swelling agent”, generating hybrids with high surface area, and as a Lewis acid co-catalytic species. TSP-Mg-imi produced excellent conversion and TONMg values, under solvent-free conditions, even at room temperature and with low catalytic loading (0.003 mol%). In terms of conversion and TONMg, TSP-Mg-imi exhibited better catalytic performance compared to a reference homogeneous system, demonstrating that the proximity between the metal centers and the nucleophilic site results in a synergistic effect during the catalytic cycle. The results of the computational study confirmed both the cooperative function and the significance of incorporating a co-catalytic species into the system.

Valentino L., Campisciano V., Célis C., Lemaur V., Lazzaroni R., Gruttadauria M., et al. (2023). Highly cross-linked bifunctional magnesium porphyrin-imidazolium bromide polymer: Unveiling the key role of co-catalysts proximity for CO2 conversion into cyclic carbonates. JOURNAL OF CATALYSIS, 428, 115143 [10.1016/j.jcat.2023.115143].

Highly cross-linked bifunctional magnesium porphyrin-imidazolium bromide polymer: Unveiling the key role of co-catalysts proximity for CO2 conversion into cyclic carbonates

Valentino L.;Campisciano V.;Gruttadauria M.;Aprile C.;Giacalone F.
2023-12-01

Abstract

Highly cross-linked materials containing an imidazolium salt and magnesium porphyrin, either in the absence (TSP-Mg-imi) or in the presence (7a and 7b) of multi-walled carbon nanotubes (MWCNTs), were synthesized and used as heterogeneous bifunctional catalysts for the conversion of CO2 into cyclic carbonates. The metalloporphyrin moiety acts both as a “covalent swelling agent”, generating hybrids with high surface area, and as a Lewis acid co-catalytic species. TSP-Mg-imi produced excellent conversion and TONMg values, under solvent-free conditions, even at room temperature and with low catalytic loading (0.003 mol%). In terms of conversion and TONMg, TSP-Mg-imi exhibited better catalytic performance compared to a reference homogeneous system, demonstrating that the proximity between the metal centers and the nucleophilic site results in a synergistic effect during the catalytic cycle. The results of the computational study confirmed both the cooperative function and the significance of incorporating a co-catalytic species into the system.
dic-2023
Valentino L., Campisciano V., Célis C., Lemaur V., Lazzaroni R., Gruttadauria M., et al. (2023). Highly cross-linked bifunctional magnesium porphyrin-imidazolium bromide polymer: Unveiling the key role of co-catalysts proximity for CO2 conversion into cyclic carbonates. JOURNAL OF CATALYSIS, 428, 115143 [10.1016/j.jcat.2023.115143].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/613373
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