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

Laura Valentino, Vincenzo Campisciano, Chloé Célis, Vincent Lemaur, Roberto Lazzaroni, Michelangelo Gruttadauria, Carmela Aprile, Francesco Giacalone

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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.

Original languageEnglish
Article number115143
Number of pages31
JournalJournal of Catalysis
Volume428
DOIs
Publication statusPublished - Dec 2023

Keywords

  • Bifunctional Heterogeneous catalyst
  • Carbon dioxide fixation
  • Carbon nanotubes
  • Cyclic carbonates
  • Mg-porphyrin

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