Direct Air Capture and Integrated Conversion of Carbon Dioxide into Cyclic Carbonates with Basic Organic Salts

Direct air capture and integrated conversion is a very attractive strategy to reduce CO2 concentration in the atmosphere. However, the existing capturing processes are technologically challenging due to the costs of the processes and the low concentration of CO2. The efficient valorization of the CO2 captured could help overcome many techno-economic limitations. Here, we present a novel economical methodology for direct air capture and conversion that is able to efficiently convert CO2 from the air into cyclic carbonates. The new approach employs commercially available basic ionic liquids, works without the need for sophisticated and expensive co-catalysts or sorbents and under mild reaction conditions. The CO2 from atmospheric air was efficiently captured by IL solution (0.98 molCO2/molIL) and, subsequently, completely converted into cyclic carbonates using epoxides or halohydrins potentially derived from biomass as substrates. A mechanism of conversion was evaluated, which helped to identify relevant reaction intermediates based on halohydrins, and consequently, a 100% selectivity was obtained using the new methodology.Funding for open access charge: CRUE-Universitat Jaume IThis work has been partially supported by University Jaume I (UJI-B2019-40 and UJI-B2020-44) and RTI2018-098233-B-C22 y C21, PID2021-124695OB-C22 (FEDER//Ministerio de Ciencia e Innovación─Agencia Estatal de Investigación). M.Z. and V.S. thank the funding received from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Individual Fellowships (GA no. 101026335). V.S. thanks Generalitat Valenciana (CIDEGENT 2018/036) for funding. The authors are grateful to the SCIC of the Universitat Jaume I for technical support. The work has been partially supported by the project TED2021-130288B-I00 funded by MCIN/AEI/10.13039/501100011033 and by EU NextGenerationEU/PRTR

Multifunctional Polymers Based on Ionic Liquid and Rose Bengal Fragments for the Conversion of CO2 to Carbonates

Supported ionic liquid-like phases (SILLPs) containing Rose Bengal (RB) units are used to develop organocatalytic systems for the cycloaddition of CO2 to epoxides. The activity of the supported RB fragments can be fine-tuned by controlling the nature of the SILLPs (i.e., substitution at the imidazolium ring, cross-linking degree of the polymeric matrix, loading, etc.). Such a catalytic system prepared from cheap, simple, and commercially available components provides high activity and stability, with no decay in activity for at least 10 days of continuous use under flow conditions.Funding for open access charge: CRUE-Universitat Jaume IFunding for open access charge: CRUE-Universitat Jaume

Chiral catalysts immobilized on achiral polymers: effect of the polymer support on the performance of the catalyst

Positive effects of the polymeric support on the performance of supported chiral catalysts, in terms of activity, stability and selectivity–enantioselectivity, have been reported when the support is properly selected and optimized opening the way to the design of more efficient catalytic systems

Imidazolium based gemini amphiphiles derived from L-valine. Structural elements and surfactant properties

Imidazolium amphiphiles often display excellent surfactants properties, while amide functionalities and chirality can implement self-assembly. The introduction of these functionalities in imidazolium gemini amphiphiles is expected to allow tuning their aggregation, achieving a higher emulsifying capacity of interest for practical applications. L-valine-derived gemini surfactants have been prepared and their aggregation investigated using NMR, UV-CD, fluorescence, LS or microscopy. The imidazolium gemini amphiphiles synthetized, presented excellent surfactant properties. The aromatic substitution pattern defines additional geometric constrains facilitating a fine tune of their properties, displaying the para-substituted compound best properties. This can be associated to facilitating the required conformational organization of polar and apolar fragments, while reducing coulombic repulsions between imizadolium rings. Two critical aggregation concentrations (CACs) were observed by fluorescence in aqueous media, with the formation of well-defined vesicles in the second step. Dynamic equilibria between aggregates of different sizes seem to be present. These gemini surfactants revealed of interest as emulsifiers for oil/water systems and for controlled fragrance delivery using (R)-limonene as a benchmark volatile compound. (C) 2021 Elsevier B.V. All rights reserved.Peer reviewe

Chiral imidazolium prolinate salts as efficient synzymatic organocatalysts for the asymmetric aldol reaction

Chiral imidazolium l-prolinate salts, providing a complex network of supramolecular interaction in a chiral environment, have been studied as synzymatic catalytic systems. They are demonstrated to be green and efficient chiral organocatalysts for direct asymmetric aldol reactions at room temperature. The corresponding aldol products were obtained with moderate to good enantioselectivities. The influence of the presence of chirality in both the imidazolium cation and the prolinate anion on the transfer of chirality from the organocatalyst to the aldol product has been studied. Moreover, interesting match/mismatch situations have been observed regarding configuration of chirality of the two components through the analysis of results for organocatalysts derived from both enantiomers of prolinate (R/S) and the trans/cis isomers for the chiral fragment of the cation. This is associated with differences in the corresponding reaction rates but also to the different tendencies for the formation of aggregates, as evidenced by nonlinear effects studies (NLE). Excellent activities, selectivities, and enantioselectivities could be achieved by an appropriate selection of the structural elements at the cation and anion

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene–phosphine complexes for the Negishi reaction under flow conditions

The combination of supported ionic liquids and immobilized NHC–Pd–RuPhos led to active and more stable systems for the Negishi reaction under continuous flow conditions than those solely based on NHC–Pd–RuPhos. The fine tuning of the NHC–Pd catalyst and the SILLPs is a key factor for the optimization of the release and catch mechanism leading to a catalytic system easily recoverable and reusable for a large number of catalytic cycles enhancing the long-term catalytic performance

Ionic liquids and continuous flow processes: a good marriage to design sustainable processes

In the last few years the use of Ionic Liquids (ILs) as alternative solvents for (bio)catalytic processes has increased substantially, and the benefits and different approaches reported to combine continuous flow systems and ILs are at the core of this overview. The synergy between both elements allowed us to highlight their great potential in manufacturing both bulk and fine chemicals by new and greener (bio)catalytic processesThis work was partially supported by MINECO, Spain (Ref: CTQ2011-28903) and Generalitat Valenciana (PROMETEO 2012/020) and UJI (P1-1B 2013-37

Free ion diffusivity and charge concentration on cross-linked Polymeric Ionic Liquid iongels films based on sulfonated zwitterion salts and Lithium ions

[EN] The properties of various mixtures of a zwitterionic ionic liquid (ZIs-1) and LiNTf 2, including their conductivity, have been studied showing how they can be adjusted through their molar composition. Conductivity tends to increase with the LiNTf2 content although it presents a minimum at the region close to the eutectic point. These mixtures also provide excellent features as liquid phases for the preparation of composite materials based on crosslinked PILs. The prepared films display excellent and tuneable properties as conducting materials, with conductivities that can be higher than 10 2 S cm 1 above 100 1C. The selected polymeric compositions show very good mechanical properties and thermal stability, even for low crosslinking degrees, along with a suitable flexibility and good transparency. The final properties of the films correlate with the composition of the monomeric mixture used and with that of the ZIs-1:LiNTf2 mixture.Financial support has been provided by MINECO (ENE/2015-69203-R and RTI2018-098233-B-C22) and Generalitat Valenciana (PROMETEO/2016/071). Technical support from the SECIC of the UJI is also acknowledged. DV thanks UNED (Costa Rica) for a predoctoral fellowship.Valverde, D.; Garcia Bernabe, A.; Andrio Balado, A.; Garcia-Verdugo, E.; Luis Lafuente, S.; Compañ Moreno, V. (2019). Free ion diffusivity and charge concentration on cross-linked Polymeric Ionic Liquid iongels films based on sulfonated zwitterion salts and Lithium ions. Physical Chemistry Chemical Physics. 21(32):17923-17932. https://doi.org/10.1039/c9cp01903kS17923179322132Etacheri, V., Marom, R., Elazari, R., Salitra, G., & Aurbach, D. (2011). Challenges in the development of advanced Li-ion batteries: a review. 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Chemoenzymatic synthesis of optically active 2-(2- or 4-substituted-1H-imidazol-1-yl)cycloalcanols. Chiral additives for (L)-proline

Enantiopure substituted imidazoles obtained by enzymatic kinetic resolution can be promising candidates as co-catalysts for aldol reactions catalysed by (L)-proline. These additives seem to form supramolecular complexes with the catalyst through the formation of H-bonds, leading to significant improvement in both the reaction rates and selectivity of the reaction. Herein, we present our results on the use of these substituted trans-2-imidazoyl-cycloalkanols as additives for the (L)-proline catalyzed direct aldol reaction between ketones and aromatic aldehydes

Preparation of nanofibers mats derived from task-specific polymeric ionic liquid for sensing and catalytic applications

Nanofibers mats derived from the task-specific functionalized polymeric ionic liquids based on homocysteine thiolactone are obtained by electrospinning them as blends with polyvinylpyrrolidone. The presence of this functional moiety allowed the post-functionalization of these mats through the aminolysis of the thiolactone ring in the presence of an amine by a thiol–alkene “click” reaction. Under controlled experimental conditions the modification can be performed introducing different functionalization and crosslinking of the electrospun fibers, while maintaining the nanostructure obtained by the electrospinning. Initial studies suggest that the nanofibers based on these functionalized polymeric ionic liquids can be used in both sensing and catalytic applications