TY - JOUR
T1 - Carbon nanotube supported aluminum porphyrin-imidazolium bromide crosslinked copolymer
T2 - A synergistic bifunctional catalyst for CO2 conversion
AU - Campisciano, Vincenzo
AU - Valentino, Laura
AU - Morena, Anthony
AU - Santiago-Portillo, Andrea
AU - Saladino, Nicolò
AU - Gruttadauria, Michelangelo
AU - Aprile, Carmela
AU - Giacalone, Francesco
N1 - Funding Information:
The authors gratefully acknowledge the University of Palermo and the Italian Ministry of Education, University and Research (MIUR) for financial support through PRIN 2017 (project no. 2017W8KNZW). Also, the authors acknowledge the University of Namur for postdoctoral fellowship. This research is supported by the F.R.S-FNRS via the funding grants GEQ U.G014.19 and EQP U.N034.17 . This research used resources of the PC2 and the MORPH-IM platforms located at the University of Namur. A. M. gratefully acknowledges the University of Palermo and University of Namur for a co-funded PhD fellowship.
Publisher Copyright:
© 2022 Elsevier Ltd
PY - 2022/3
Y1 - 2022/3
N2 - The increased awareness of the catastrophic consequences caused by the accumulation of greenhouse gases into the atmosphere has generated a large mobilization aimed at CO2 mitigation. Herein, in the spirit of the transformation of a waste as CO2 into value added products, we propose an efficient preparation of two different hybrid systems based on aluminum chloride tetrastyrylporphyrin (TSP-Al-Cl) and 1,4-butanediyl-3,3′-bis-1-vinylimidazolium dibromide copolymerized in the presence (MWCNT-TSP-AlCl-imi) and in absence (TSP-AlCl-imi) of multi-walled carbon nanotubes (MWCNTs) for the CO2 utilization in the synthesis of cyclic carbonates. The so-prepared materials have been thoroughly characterized by means of several spectroscopic and analytical techniques. The MWCNT-TSP-AlCl-imi heterogenous catalyst enabled the highly efficient chemical transformation of CO2 and epoxides into cyclic carbonates with high turnover number (TON) and frequency (TOF) values at low temperature down to 30 °C in solvent-free conditions. MWCNT-TSP-AlCl-imi proved to be a very stable and reusable heterogeneous catalyst in consecutive cycles without the need of any reactivation procedure and no leaching phenomena. Furthermore, the optimal morphology of MWCNT-TSP-AlCl-imi, with the crosslinked polymer uniformly distributed onto MWCNTs backbone, resulted in a more active catalyst with a TON double than the unsupported one. The enhanced activity of MWCNT-TSP-AlCl-imi can be ascribed to its higher surface area that permits fully accessible catalytic sites. Interestingly, MWCNT-TSP-AlCl-imi also showed a catalytic activity comparable to a reference homogeneous catalytic system, proving that synergism occurred between the metal centers and the nucleophilic sites due to their close proximity.
AB - The increased awareness of the catastrophic consequences caused by the accumulation of greenhouse gases into the atmosphere has generated a large mobilization aimed at CO2 mitigation. Herein, in the spirit of the transformation of a waste as CO2 into value added products, we propose an efficient preparation of two different hybrid systems based on aluminum chloride tetrastyrylporphyrin (TSP-Al-Cl) and 1,4-butanediyl-3,3′-bis-1-vinylimidazolium dibromide copolymerized in the presence (MWCNT-TSP-AlCl-imi) and in absence (TSP-AlCl-imi) of multi-walled carbon nanotubes (MWCNTs) for the CO2 utilization in the synthesis of cyclic carbonates. The so-prepared materials have been thoroughly characterized by means of several spectroscopic and analytical techniques. The MWCNT-TSP-AlCl-imi heterogenous catalyst enabled the highly efficient chemical transformation of CO2 and epoxides into cyclic carbonates with high turnover number (TON) and frequency (TOF) values at low temperature down to 30 °C in solvent-free conditions. MWCNT-TSP-AlCl-imi proved to be a very stable and reusable heterogeneous catalyst in consecutive cycles without the need of any reactivation procedure and no leaching phenomena. Furthermore, the optimal morphology of MWCNT-TSP-AlCl-imi, with the crosslinked polymer uniformly distributed onto MWCNTs backbone, resulted in a more active catalyst with a TON double than the unsupported one. The enhanced activity of MWCNT-TSP-AlCl-imi can be ascribed to its higher surface area that permits fully accessible catalytic sites. Interestingly, MWCNT-TSP-AlCl-imi also showed a catalytic activity comparable to a reference homogeneous catalytic system, proving that synergism occurred between the metal centers and the nucleophilic sites due to their close proximity.
KW - Al-porphyrin
KW - Bifunctional catalyst
KW - Carbon dioxide fixation
KW - Carbon nanotubes
KW - Cyclic carbonates
UR - http://www.scopus.com/inward/record.url?scp=85122988227&partnerID=8YFLogxK
U2 - 10.1016/j.jcou.2022.101884
DO - 10.1016/j.jcou.2022.101884
M3 - Article
AN - SCOPUS:85122988227
SN - 2212-9820
VL - 57
JO - Journal of CO2 Utilization
JF - Journal of CO2 Utilization
M1 - 101884
ER -