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Projeto de investigação
From ION Gels to AEROPILs - A poly(ionic liquid) tailored platform for CO2 utilization and beyond
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Publicações
Sulfonic Acid-Functionalized (Bio)Materials as Catalysts for Efficient Amide Bond Synthesis
Publication . Pereira, Joana R.; Corvo, Marta C.; Peixoto, Andreia F.; Aguiar-Ricardo, Ana; Marques, M. Manuel B.; DQ - Departamento de Química; LAQV@REQUIMTE; DCM - Departamento de Ciência dos Materiais; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); Wiley - VCH Verlag GmbH & CO. KGaA
Sulfonic acid carbon-(bio)based and natural clays-based catalysts were prepared and investigated for the first time as heterogeneous catalysts for amide bond synthesis by a Ritter reaction. The different SO3H-catalysts were screened using benzyl alcohol and acetonitrile as model substrates, and MWCNT-CSP revealed to be an efficient catalyst, affording the amide in 75 % yield. The practical utility of the catalysts was demonstrated by a diverse range of amides, obtained from alcohols and nitriles, in moderate to good yields. Biomass derived platform alcohols, such as 5-HMF and furfuryl alcohol, were also tested as potential building blocks for the synthesis of biopolymers. The SO3H-catalysts revealed to be a highly efficient and environmentally friendly alternative to the conventional acid catalysts commonly used in the Ritter reaction.
Poly(ionic liquid)-based aerogels for continuous-flow CO2 upcycling
Publication . Barrulas, Raquel V.; Tinajero, Cristopher; Ferreira, Diogo P. N.; Illanes-Bordomás, Carlos; Sans, Victor; Carrott, Manuela Ribeiro; García-González, Carlos A.; Zanatta, Marcileia; Corvo, Marta C.; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); DCM - Departamento de Ciência dos Materiais; Elsevier BV
The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable of capture and conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts for processes at or near atmospheric pressure. PILs industrial application poses challenges due to the low porosity of PIL, the limited batch conversion capacity, and the difficulties in reuse. To overcome these limitations, we herein propose the use of AEROPILs catalysts obtained from the integration of PILs in chitosan-based aerogels. These cost-effective highly porous materials have unique and tuneable porous properties making them not only ideal sustainable CO2 sorbents but also promising heterogeneous catalysts. While AEROPILs show moderate yields for CO2 conversion in batch mode, high catalytic activity was achieved when AEROPILs were used to catalyse the CO2 cycloaddition reaction to epoxides in packed-bed reactors operated under continuous flow. The catalytic activity and stability were maintained over 60 h without activity loss, and high productivity (space-time yield of 21.18 gprod h−1 L−1). This research reveals the pioneering use of AEROPILs to efficiently upcycle CO2 into cyclic carbonate under a continuous flow setup.
Tuning basic poly(ionic liquid) solutions towards atmospheric pressure CO2 capture
Publication . Silva, Ana; Barrulas, Raquel V.; Corvo, Marta C.; Zanatta, Marcileia; DCM - Departamento de Ciência dos Materiais; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); Elsevier BV
Ionic liquids and poly(ionic liquid)s are interesting materials for CO2 capture, however, the deployment of their industrial application has been delayed on account of economic and technical issues that demand further optimization. The control over viscosity has serious consequences over the process, therefore, this work is focused on the study of imidazolium and pyrrolidinium-derived ILs and PILs with basic anions, such as acetate, hydroxide, and imidazolate that were synthesized and characterized by NMR, ATR-FTIR, TGA, and DSC. Different solvents and concentrations were tested in the preparation of PIL and IL solutions, which were used to capture CO2 by bubbling this gas at room temperature and atmospheric pressure (1 atm). The evaluation of the CO2 sorption capacity of each sample was carried out through the analysis of quantitative 13C NMR. The poly(1-vinyl-3-ethylimidazolium) acetate showed and sorption capacity of 5.68 mmol CO2/g PIL, and also the capacity to capture CO2 from exhaust gas mixture and the possibility to be recycled at least 5 times.
Mechanistic insights on ionic liquid and poly(ionic liquid) solutions for CO2 capture and cycloaddition reactions
Publication . Barrulas, Raquel V.; Barão, Rodrigo M.; Bernardes, Carlos E.S.; Zanatta, Marcileia; Corvo, Marta C.; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); DCM - Departamento de Ciência dos Materiais; Elsevier
This study explores the potential of ionic liquids (ILs) and poly(ionic liquid)s (PILs) for CO2 capture and conversion. Using molecular dynamics simulations in DMSO solutions, we found that ILs and PILs exhibit similar CO2 sorption, with the ILs [BMIM][OAc] and [P4,4,4,4][OAc] showing the highest capacities. Bromide-derived PILs enhance aqueous sorption through cage formation, unlike ILs. We also examined the catalytic efficiency of PILs P[VBA]Cl and P[VBP]Cl, and IL [BA]Cl in CO2 cycloaddition reactions. DMSO decreases IL catalytic activity but improves P[VBA]Cl's performance. These findings suggest that higher CO2 sorption in ILs does not always correlate with better catalytic results. In conclusion, IL and PIL solutions in DMSO demonstrate significant potential for the effective modulation of material properties.
Flexographic Printed Flexible Thermochromic Stickers for Smart Sensing Applications
Publication . Morais, M.; Figueira, J.; Corvo, M. C.; Peixoto, M.; Oliveira, Duarte Belo de; Gonçalves, A.; Fortunato, E.; Martins, R.; Carlos, E.; Pinto, J. V.; DCM - Departamento de Ciência dos Materiais; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); John Wiley and Sons Ltd
The growing demand for thermochromic materials in areas such as food packaging requires the development of fast-response and extended-life materials. The use of metal cation-ionic liquid complexes is increasing due to the easiness to tailor their properties, leading to changes in thermochromic response. This work presents the synthesis and introduction of thermochromic 1-butyl-3-methylimidazolium chloride and 4-chloronickelate ([BMIm]2[NiCl4]) complexes into water-based inks. Formulations with varying concentrations of complexes (10–40 wt.%) are printed on tags thorugh a roll-to-roll process and tested between 30–45 °C. Also, films with one to five layers are analyzed for color contrast and different encapsulating materials are studied to improve the thermochromic films' robustness. The optimal films, with three layers of ink with 40 wt.% complexes encapsulated with Fixomull Transparent present enhanced color contrast and fast response time. Red-green-blue analysis is performed on these films, revealing a blue/red ratio of 1.7 after heating at 40 °C for 30 min. This work paves the way for developing flexible stickers with fast response and high contrast. The innovative and straightforward thermochromic inks' production process and compatibility with large-scale manufacturing show their promising future as cost-effective stickers for smart packaging applications, such as visual indicators of ideal food consumption temperatures.
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Entidade financiadora
Fundação para a Ciência e a Tecnologia
Programa de financiamento
CEEC IND4ed
Número da atribuição
2021.03255.CEECIND/CP1657/CT0014