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In the last five years, the use of deep eutectic solvents (DES) have been opening new perspectives towards the creation of novel ionic soft materials as alternatives to expensive ionic liquids. This Mini-Review highlights the progress and advances in soft ionic materials or gels, mostly composed by a DES immobilized within difference matrices, such as linear polymers, polymer networks, biopolymers, supramolecular compounds or organosilane networks. By taking advantage of the DES characteristics and properties in the solid state, this building system delivers a variety of tailor-made materials showing different functionalities (ionic conductivity, self-healing, stretchability and pH-responsiveness) and offers a way to circumvent drawbacks related to shaping and risk of leakage in many technological applications. In this context, we provide a judicious analysis of these emerging ionic soft materials, their properties and applications open in energy, (bio)electronics, drug delivery, analytical chemistry, and wastewater treatment. Perspectives and opportunities for future research directions on this blossoming field are also discussed.
Liliana C. Tomé; David Mecerreyes. Emerging Ionic Soft Materials Based on Deep Eutectic Solvents. The Journal of Physical Chemistry B 2020, 124, 8465 -8478.
AMA StyleLiliana C. Tomé, David Mecerreyes. Emerging Ionic Soft Materials Based on Deep Eutectic Solvents. The Journal of Physical Chemistry B. 2020; 124 (39):8465-8478.
Chicago/Turabian StyleLiliana C. Tomé; David Mecerreyes. 2020. "Emerging Ionic Soft Materials Based on Deep Eutectic Solvents." The Journal of Physical Chemistry B 124, no. 39: 8465-8478.
Iongels have attracted much attention over the years as ion‐conducting soft materials for applications in several technologies including stimuli‐responsive drug release and flexible (bio)electronics. Nowadays, iongels with additional functionalities such as electronic conductivity, self‐healing, thermo‐responsiveness, or biocompatibility are actively being searched for high demanding applications. In this work, a simple and rapid synthetic pathway to prepare elastic and thermoreversible iongels is presented. These iongels are prepared by supramolecular crosslinking between polyphenols biomolecules with a hydroxyl‐rich biocompatible polymer such as poly(vinyl alcohol) (PVA) in the presence of ionic liquids. Using this strategy, a variety of iongels are obtained by combining different plant‐derived polyphenol compounds (PhC) such as gallic acid, pyrogallol, and tannic acid with imidazolium‐based ionic liquids, namely 1‐ethyl‐3‐methylimidazolium dicyanamide and 1‐ethyl‐3‐methylimidazolium bromide. A suite of characterization tools is used to study the structural, morphological, mechanical, rheological, and thermal properties of the supramolecular iongels. These iongels can withstand large deformations (40% under compression) with full recovery, revealing reversible transitions from solid to liquid state between 87 and 125 °C. Finally, the polyphenol‐based thermoreversible iongels show appropriated properties for their potential application as printable electrolytes for bioelectronics.
Gisela C. Luque; Matías L. Picchio; Ana P. S. Martins; Antonio Dominguez-Alfaro; Liliana C. Tomé; David Mecerreyes; Roque J. Minari. Elastic and Thermoreversible Iongels by Supramolecular PVA/Phenol Interactions. Macromolecular Bioscience 2020, 20, 1 .
AMA StyleGisela C. Luque, Matías L. Picchio, Ana P. S. Martins, Antonio Dominguez-Alfaro, Liliana C. Tomé, David Mecerreyes, Roque J. Minari. Elastic and Thermoreversible Iongels by Supramolecular PVA/Phenol Interactions. Macromolecular Bioscience. 2020; 20 (11):1.
Chicago/Turabian StyleGisela C. Luque; Matías L. Picchio; Ana P. S. Martins; Antonio Dominguez-Alfaro; Liliana C. Tomé; David Mecerreyes; Roque J. Minari. 2020. "Elastic and Thermoreversible Iongels by Supramolecular PVA/Phenol Interactions." Macromolecular Bioscience 20, no. 11: 1.
Clean and sustainable energy production has become a key global issue concerning the world’s energy shortage and environmental problems. Despite the recognized potential of biohydrogen (bioH2) for sustainable development, there are still issues regarding its production and purification, such as the elimination of CO2, N2, and other impurities (H2O and H2S), so that an enriched H2 stream can be obtained for efficient energy generation. The use of poly(ionic liquid)s (PILs) and their derived composite materials incorporating ionic liquids (PIL–IL) has been considered a highly promising strategy to design membranes with improved CO2 separation. In this study, membranes of pyrrolidinium-based PILs containing symmetric or asymmetric fluorosulfonyl-derived anions, namely, bis(fluorosulfonyl)amide ([FSI]−), (trifluoromethyl)sulfonyl-N-cyanoamide ([TFSAM]−), and (trifluoromethyl)sulfonyl-N-trifluoroacetamide ([TSAC]−), were prepared by the incorporation of different amounts of structurally similar ILs. The PIL–IL membranes were characterized by different techniques (thermogravimetric analysis, differential scanning calorimetry, Fourier-transform infrared, and Raman), and their CO2/H2 and H2/N2 separation performances were investigated. Higher CO2/H2 selectivities were obtained for PIL FSI–40 [C2mim][FSI] (αCO2/H2 = 9.0) and PIL TFSAM–40 [C2mim][TFSAM] (αCO2/H2 = 7.1) compared to those of PIL–IL membranes containing the conventional [TFSI]− anion at similar or even higher amounts of IL incorporation.
Andreia S. L. Gouveia; Eglè Malcaitè; Elena I. Lozinskaya; Alexander S. Shaplov; Liliana C. Tomé; Isabel M. Marrucho. Poly(ionic liquid)–Ionic Liquid Membranes with Fluorosulfonyl-Derived Anions: Characterization and Biohydrogen Separation. ACS Sustainable Chemistry & Engineering 2020, 8, 7087 -7096.
AMA StyleAndreia S. L. Gouveia, Eglè Malcaitè, Elena I. Lozinskaya, Alexander S. Shaplov, Liliana C. Tomé, Isabel M. Marrucho. Poly(ionic liquid)–Ionic Liquid Membranes with Fluorosulfonyl-Derived Anions: Characterization and Biohydrogen Separation. ACS Sustainable Chemistry & Engineering. 2020; 8 (18):7087-7096.
Chicago/Turabian StyleAndreia S. L. Gouveia; Eglè Malcaitè; Elena I. Lozinskaya; Alexander S. Shaplov; Liliana C. Tomé; Isabel M. Marrucho. 2020. "Poly(ionic liquid)–Ionic Liquid Membranes with Fluorosulfonyl-Derived Anions: Characterization and Biohydrogen Separation." ACS Sustainable Chemistry & Engineering 8, no. 18: 7087-7096.
Polymeric membranes either containing, or built from, ionic liquids (ILs) are of great interest for enhanced CO2/light gas separation due to the stronger affinity of ILs toward quadrupolar CO2 molecules, and hence, high CO2 solubility selectivity. Herein, we report the development of a series of four novel anionic poly(IL)-IL composite membranes via a photopolymerization method for effective CO2 separation. Interestingly, these are the first examples of anionic poly(IL)-IL composite systems, in which the poly(IL) component has delocalized sulfonimide anions pendant from the polymer backbone with imidazolium cations as “free” counterions. Two types of photopolymerizable methacryloxy-based IL monomers (MILs) with highly delocalized anions (–SO2–N(-)–SO2–CF3 and –SO2–N(-)–SO2–C7H7) and mobile imidazolium ([C2mim]+) counter cations were successfully synthesized and photopolymerized with two distinct amounts of free IL containing the same structural cation ([C2mim][Tf2N]) and 20 wt% PEGDA crosslinker, to serve as a composite matrix. The structure-property relationships of the four newly developed anionic poly(IL)-IL composite membranes were extensively characterized by TGA, DSC, and XRD analysis. All of the newly developed anionic poly(IL)-IL composite membranes exhibited superior CO2/CH4 and CO2/N2 selectivities together with moderate CO2/H2 selectivity and reasonable CO2 permeabilities. The membrane with an optimal composition and polymer architecture (MIL-C7H7/PEGDA(20%)/IL(1eq.)) reaches the 2008 Robeson upper bound limit of CO2/CH4, due to the simultaneous improvement in permeability and selectivity (CO2 permeability ~ 20 barrer and αCO2/CH4 ~119). This study provides a promising strategy to explore the benefits of anionic poly(IL)-IL composites to separate CO2 from flue gas, natural gas, and syngas streams and open up new possibilities in the polymer membrane design with strong candidate materials for practical applications.
Irshad Kammakakam; Jason E. Bara; Enrique M. Jackson; Josu Lertxundi; David Mecerreyes; Liliana C. Tomé. Tailored CO2-Philic Anionic Poly(ionic liquid) Composite Membranes: Synthesis, Characterization, and Gas Transport Properties. ACS Sustainable Chemistry & Engineering 2020, 8, 5954 -5965.
AMA StyleIrshad Kammakakam, Jason E. Bara, Enrique M. Jackson, Josu Lertxundi, David Mecerreyes, Liliana C. Tomé. Tailored CO2-Philic Anionic Poly(ionic liquid) Composite Membranes: Synthesis, Characterization, and Gas Transport Properties. ACS Sustainable Chemistry & Engineering. 2020; 8 (15):5954-5965.
Chicago/Turabian StyleIrshad Kammakakam; Jason E. Bara; Enrique M. Jackson; Josu Lertxundi; David Mecerreyes; Liliana C. Tomé. 2020. "Tailored CO2-Philic Anionic Poly(ionic liquid) Composite Membranes: Synthesis, Characterization, and Gas Transport Properties." ACS Sustainable Chemistry & Engineering 8, no. 15: 5954-5965.
Iongel-based CO2 separation membranes were prepared by fast (< 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C2mim]+ cation and anions such as [TFSI]−, [FSI]−, [C(CN)3]− and [B(CN)4]−. The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and free-standing iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO2 solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO2 solubility, were found to be strictly dependent on the IL content and the anion’s nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA–C(CN)3 iongels presented the highest CO2 solubility values ranging from 72 to 80 mmol/g. Single CO2 permeabilities of 583 ± 29 Barrer and ideal CO2/N2 selectivities of 66 ± 3 were obtained with the PEGDA–70 C(CN)3 iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO2 separation.
Ana P. S. Martins; Asier Fdz De Añastro; Jorge L. Olmedo-Martínez; Ana R. Nabais; Luísa A. Neves; David Mecerreyes; Liliana C. Tomé. Influence of Anion Structure on Thermal, Mechanical and CO2 Solubility Properties of UV-Cross-Linked Poly(ethylene glycol) Diacrylate Iongels. Membranes 2020, 10, 46 .
AMA StyleAna P. S. Martins, Asier Fdz De Añastro, Jorge L. Olmedo-Martínez, Ana R. Nabais, Luísa A. Neves, David Mecerreyes, Liliana C. Tomé. Influence of Anion Structure on Thermal, Mechanical and CO2 Solubility Properties of UV-Cross-Linked Poly(ethylene glycol) Diacrylate Iongels. Membranes. 2020; 10 (3):46.
Chicago/Turabian StyleAna P. S. Martins; Asier Fdz De Añastro; Jorge L. Olmedo-Martínez; Ana R. Nabais; Luísa A. Neves; David Mecerreyes; Liliana C. Tomé. 2020. "Influence of Anion Structure on Thermal, Mechanical and CO2 Solubility Properties of UV-Cross-Linked Poly(ethylene glycol) Diacrylate Iongels." Membranes 10, no. 3: 46.
Bearing in mind that Metal Organic Frameworks (MOFs) have remarkable CO2 adsorption selectivity and Mixed Matrix Membranes (MMMs) have been identified as potential solution for advancing the current state of the art of membrane separation technology, this work investigates the effect of combining a MOF, with high adsorption properties towards CO2 when compared to CH4 (MOF-5), with a blend of poly(ionic liquid)/ionic liquid (PIL/IL) for biogas upgrading. The blend system consisted of a pyrrolidinium-based PIL, poly([Pyr11][Tf2N]), and a free imidazolium-based IL, [C2mim][BETI]. The MOF-5 was incorporated at different loadings (10, 20, 30 wt%), and MMMs were prepared by solvent evaporation and characterized by diverse techniques (FTIR, SEM, TGA, puncture tests and single gas transport). The results showed that the free IL is miscible with the PIL, while MOF-5 particles were uniformly dispersed into the PIL/IL matrix. The formed PIL/IL/MOF-5 membranes revealed suitable thermal stability (Tonset up to 656 K) for biogas upgrading processes, but a loss of mechanical stability was found after the incorporation of MOF-5, and thus more rigid and fragile membranes were obtained. At 30 wt% of MOF-5 loading the CO2 permeability increased 133% when compared to that of the pristine PIL/IL membrane, mainly due to the adsorption capacity of the MOF, as well as its porous structure. The presence of a porous structure may also be the reason why the ideal selectivity decreases by 88% for the MMM with the highest loading. It was possible to demonstrate the relevance of studying different components within the polymeric matrix in order to assess not only thermal, mechanical and chemical properties, but also gas transport response.
Adriana M. Sampaio; Ana Rita Nabais; Liliana C. Tomé; Luísa A. Neves. Impact of MOF-5 on Pyrrolidinium-Based Poly(ionic liquid)/Ionic Liquid Membranes for Biogas Upgrading. Industrial & Engineering Chemistry Research 2019, 59, 308 -317.
AMA StyleAdriana M. Sampaio, Ana Rita Nabais, Liliana C. Tomé, Luísa A. Neves. Impact of MOF-5 on Pyrrolidinium-Based Poly(ionic liquid)/Ionic Liquid Membranes for Biogas Upgrading. Industrial & Engineering Chemistry Research. 2019; 59 (1):308-317.
Chicago/Turabian StyleAdriana M. Sampaio; Ana Rita Nabais; Liliana C. Tomé; Luísa A. Neves. 2019. "Impact of MOF-5 on Pyrrolidinium-Based Poly(ionic liquid)/Ionic Liquid Membranes for Biogas Upgrading." Industrial & Engineering Chemistry Research 59, no. 1: 308-317.
Poly(ionic liquid)s (PIL) have emerged as a class of versatile polyelectrolites, that can be used to prepare new materials able to achieve superior performances compared to conventional polymers. The combination of PILs with ionic liquids (ILs) may serve as a suitable matrix for the preparation of membranes for gas separation. In this work, mixed matrix membranes (MMMs) combining a pyrrolidinium-based PIL, an IL and three highly CO2-selective metal organic frameworks (MOFs) were prepared. The different MOFs (MIL-53(Al), Cu3(BTC)2 and ZIF-8) were used as fillers, aiming to maximize the membranes performance towards the purification of syngas. The influence of different MOFs and loadings (0, 10, 20 and 30 wt.%) on the thermal and mechanical stabilities of the membranes and their performance in terms of CO2 permeability and CO2/H2 ideal selectivity was assessed. The compatibility between the materials was confirmed by SEM-EDS and FTIR spectroscopy. The prepared MMMs revealed to be thermally stable within the temperature range of the syngas stream, with a loss of mechanical stability upon the MOF incorporation. The increasing MOF content in the MMMs, resulted in an improvement of both CO2 permeability and CO2/H2 ideal selectivity. Among the three MOFs studied, membranes based on ZIF-8 showed the highest permeabilities (up to 97.2 barrer), while membranes based on MIL-53(Al) showed the highest improvement in selectivity (up to 13.3). Remarkably, all permeation results surpass the upper bound limit for the CO2/H2 separation, showing the membranes potential for the desired gas separation.
Ana Nabais; Ana P. S. Martins; Vítor D. Alves; João Crespo; Isabel M. Marrucho; Liliana C. Tomé; Luísa A. Neves. Poly(ionic liquid)-based engineered mixed matrix membranes for CO2/H2 separation. Separation and Purification Technology 2019, 222, 168 -176.
AMA StyleAna Nabais, Ana P. S. Martins, Vítor D. Alves, João Crespo, Isabel M. Marrucho, Liliana C. Tomé, Luísa A. Neves. Poly(ionic liquid)-based engineered mixed matrix membranes for CO2/H2 separation. Separation and Purification Technology. 2019; 222 ():168-176.
Chicago/Turabian StyleAna Nabais; Ana P. S. Martins; Vítor D. Alves; João Crespo; Isabel M. Marrucho; Liliana C. Tomé; Luísa A. Neves. 2019. "Poly(ionic liquid)-based engineered mixed matrix membranes for CO2/H2 separation." Separation and Purification Technology 222, no. : 168-176.
The development of efficient carbon dioxide capture and separation technologies is at the fore front of the priorities in the climate change policies. Poly(ionic liquid)s (PILs) have been emerging as extremely promising materials for the fabrication of membranes for CO2 separation. This work is a step forward to evaluate the effect of the PIL-based copolymers chemical structure in the preparation and performance of membranes for CO2/N2 separation. In particular, imidazolium-based homo and copolymers were synthesized by RAFT co-polymerization of different imidazolium salts and characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) analysis. The membrane forming ability of the synthesized PILs, as well as the influence of different side chain groups (ethyl, pentyl, benzyl and napthyl) at imidazolium ring, were evaluated using the solvent casting technique. In order to improve membrane forming ability and CO2 separation performance, different amounts of free ionic liquid (IL), [C2mim][NTf2], were added into the synthesized homo and copolymers, and PIL–IL composite membranes were prepared. The CO2 and N2 permeation properties of the obtained free standing PIL–IL membranes were measured at 20 ºC and 100 kPa and the results obtained compared through the Robeson plot.
Pothanagandhi Nellepalli; Liliana C. Tomé; Kari Vijayakrishna; Isabel M. Marrucho. Imidazolium-Based Copoly(Ionic Liquid) Membranes for CO2/N2 Separation. Industrial & Engineering Chemistry Research 2019, 58, 2017 -2026.
AMA StylePothanagandhi Nellepalli, Liliana C. Tomé, Kari Vijayakrishna, Isabel M. Marrucho. Imidazolium-Based Copoly(Ionic Liquid) Membranes for CO2/N2 Separation. Industrial & Engineering Chemistry Research. 2019; 58 (5):2017-2026.
Chicago/Turabian StylePothanagandhi Nellepalli; Liliana C. Tomé; Kari Vijayakrishna; Isabel M. Marrucho. 2019. "Imidazolium-Based Copoly(Ionic Liquid) Membranes for CO2/N2 Separation." Industrial & Engineering Chemistry Research 58, no. 5: 2017-2026.
Considering the high potential of hydrogen (H2) as a clean energy carrier, the implementation of high performance and cost-effective biohydrogen (bioH2) purification techniques is of vital importance, particularly in fuel cell applications. As membrane technology is a potentially energy-saving solution to obtain high-quality biohydrogen, the most promising poly(ionic liquid) (PIL)–ionic liquid (IL) composite membranes that had previously been studied by our group for CO2/N2 separation, containing pyrrolidinium-based PILs with fluorinated or cyano-functionalized anions, were chosen as the starting point to explore the potential of PIL–IL membranes for CO2/H2 separation. The CO2 and H2 permeation properties at the typical conditions of biohydrogen production (T = 308 K and 100 kPa of feed pressure) were measured and discussed. PIL–IL composites prepared with the [C(CN)3]− anion showed higher CO2/H2 selectivity than those containing the [NTf2]− anion. All the membranes revealed CO2/H2 separation performances above the upper bound for this specific separation, highlighting the composite incorporating 60 wt % of [C2mim][C(CN)3] IL.
Andreia S. L. Gouveia; Lucas Ventaja; Liliana C. Tomé; Isabel M. Marrucho. Towards Biohydrogen Separation Using Poly(Ionic Liquid)/Ionic Liquid Composite Membranes. Membranes 2018, 8, 124 .
AMA StyleAndreia S. L. Gouveia, Lucas Ventaja, Liliana C. Tomé, Isabel M. Marrucho. Towards Biohydrogen Separation Using Poly(Ionic Liquid)/Ionic Liquid Composite Membranes. Membranes. 2018; 8 (4):124.
Chicago/Turabian StyleAndreia S. L. Gouveia; Lucas Ventaja; Liliana C. Tomé; Isabel M. Marrucho. 2018. "Towards Biohydrogen Separation Using Poly(Ionic Liquid)/Ionic Liquid Composite Membranes." Membranes 8, no. 4: 124.
In this work, poly(ionic liquid)–ionic liquid (PIL–IL) composite membranes were prepared using the solvent casting technique. The studied PILs have pyrrolidinium polycation backbone ([Pyr11]+), while the five ILs display either an imidazolium ([C2mim]+) or a pyrrolidinium ([Pyr14]+) based cation. Both the PIL and IL components comprised cyano-functionalized anions ([N(CN)2]–, [C(CN)3]– or [B(CN)4]–), being the anion for each component different from one another. The use of the [NTf2]– anion was also tested for comparison. Several experimental conditions for the solvent casting procedure were tested in order to prepare homogenous and free standing PIL–IL composite membranes. The CO2 and N2 permeation properties (permeability, diffusivity and solubility) were evaluated at a fixed temperature (293 K) and constant trans-membrane pressure differential (100 kPa) using a time-lag apparatus, so that trends regarding the different anions either on the PIL or IL could be obtained and evaluated. From all 42 PIL–IL combinations tested, 21 were suitable membranes (homogeneous and free standing) for gas permeation experiments and 4 of them were on top or surpassed the 2008 Robeson upper bound for CO2/N2 separation. The best performance membranes contain the [C(CN)3]– and [B(CN)4]– anions, enlightening therefore the promise these anions entail for future high performance membranes for post-combustion CO2 separation.
Raquel M. Teodoro; Liliana C. Tomé; Daniele Mantione; David Mecerreyes; Isabel M. Marrucho. Mixing poly(ionic liquid)s and ionic liquids with different cyano anions: Membrane forming ability and CO 2 /N 2 separation properties. Journal of Membrane Science 2018, 552, 341 -348.
AMA StyleRaquel M. Teodoro, Liliana C. Tomé, Daniele Mantione, David Mecerreyes, Isabel M. Marrucho. Mixing poly(ionic liquid)s and ionic liquids with different cyano anions: Membrane forming ability and CO 2 /N 2 separation properties. Journal of Membrane Science. 2018; 552 ():341-348.
Chicago/Turabian StyleRaquel M. Teodoro; Liliana C. Tomé; Daniele Mantione; David Mecerreyes; Isabel M. Marrucho. 2018. "Mixing poly(ionic liquid)s and ionic liquids with different cyano anions: Membrane forming ability and CO 2 /N 2 separation properties." Journal of Membrane Science 552, no. : 341-348.
Liliana C. Tomé; Diogo C. Guerreiro; Raquel M. Teodoro; Vitor Delgado Alves; Isabel Marrucho. Effect of polymer molecular weight on the physical properties and CO2/N2 separation of pyrrolidinium-based poly(ionic liquid) membranes. Journal of Membrane Science 2018, 549, 267 -274.
AMA StyleLiliana C. Tomé, Diogo C. Guerreiro, Raquel M. Teodoro, Vitor Delgado Alves, Isabel Marrucho. Effect of polymer molecular weight on the physical properties and CO2/N2 separation of pyrrolidinium-based poly(ionic liquid) membranes. Journal of Membrane Science. 2018; 549 ():267-274.
Chicago/Turabian StyleLiliana C. Tomé; Diogo C. Guerreiro; Raquel M. Teodoro; Vitor Delgado Alves; Isabel Marrucho. 2018. "Effect of polymer molecular weight on the physical properties and CO2/N2 separation of pyrrolidinium-based poly(ionic liquid) membranes." Journal of Membrane Science 549, no. : 267-274.
The CO2 and N2 permeation properties of ionic liquids (ILs) based on a common imidazolium cation and different fluorinated anions were measured using supported ionic liquid membranes (SILMs).
Andreia S. L. Gouveia; Liliana C. Tomé; Elena I. Lozinskaya; Alexander S. Shaplov; Yakov S. Vygodskii; Isabel M. Marrucho. Exploring the effect of fluorinated anions on the CO2/N2 separation of supported ionic liquid membranes. Physical Chemistry Chemical Physics 2017, 19, 28876 -28884.
AMA StyleAndreia S. L. Gouveia, Liliana C. Tomé, Elena I. Lozinskaya, Alexander S. Shaplov, Yakov S. Vygodskii, Isabel M. Marrucho. Exploring the effect of fluorinated anions on the CO2/N2 separation of supported ionic liquid membranes. Physical Chemistry Chemical Physics. 2017; 19 (42):28876-28884.
Chicago/Turabian StyleAndreia S. L. Gouveia; Liliana C. Tomé; Elena I. Lozinskaya; Alexander S. Shaplov; Yakov S. Vygodskii; Isabel M. Marrucho. 2017. "Exploring the effect of fluorinated anions on the CO2/N2 separation of supported ionic liquid membranes." Physical Chemistry Chemical Physics 19, no. 42: 28876-28884.
Herein, seven anions including four imide-based and two sulfonate anions are considered and compared.
Andreia S.L. Gouveia; Carlos E. S. Bernardes; Liliana C. Tomé; Elena I. Lozinskaya; Yakov S. Vygodskii; Alexander S. Shaplov; José N. Canongia Lopes; Isabel M. Marrucho. Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model. Physical Chemistry Chemical Physics 2017, 19, 29617 -29624.
AMA StyleAndreia S.L. Gouveia, Carlos E. S. Bernardes, Liliana C. Tomé, Elena I. Lozinskaya, Yakov S. Vygodskii, Alexander S. Shaplov, José N. Canongia Lopes, Isabel M. Marrucho. Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model. Physical Chemistry Chemical Physics. 2017; 19 (43):29617-29624.
Chicago/Turabian StyleAndreia S.L. Gouveia; Carlos E. S. Bernardes; Liliana C. Tomé; Elena I. Lozinskaya; Yakov S. Vygodskii; Alexander S. Shaplov; José N. Canongia Lopes; Isabel M. Marrucho. 2017. "Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model." Physical Chemistry Chemical Physics 19, no. 43: 29617-29624.
Crosslinked pyrrolidinium-based poly(ionic liquids) (Pyrr-PILs) were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME) sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and homogeneously coated on a steel wire by using a very simple procedure. The resulting coatings showed a high thermal stability, with decomposition temperatures above 350 °C, excellent film stability, and lifetime of over 100 injections. The performance of these PIL-based SPME fibers was evaluated using a mixture of eleven organic compounds with different molar volumes and chemical functionalities (alcohols, ketones, and monoterpenes). The Pyrr-PIL fibers were obtained as dense film coatings, with 67 μm thickness, with an overall sorption increase of 90% and 55% as compared to commercial fibers of Polyacrylate (85 μm) (PA85) and Polydimethylsiloxane (7 μm) (PDMS7) coatings, respectively. A urine sample doped with the sample mixture was used to study the matrix effect and establish relative recoveries, which ranged from 60.2% to 104.1%.
David J. S. Patinha; Liliana C. Tomé; Mehmet Isik; David Mecerreyes; Armando J. D. Silvestre; Isabel M. Marrucho. Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings. Materials 2017, 10, 1094 .
AMA StyleDavid J. S. Patinha, Liliana C. Tomé, Mehmet Isik, David Mecerreyes, Armando J. D. Silvestre, Isabel M. Marrucho. Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings. Materials. 2017; 10 (9):1094.
Chicago/Turabian StyleDavid J. S. Patinha; Liliana C. Tomé; Mehmet Isik; David Mecerreyes; Armando J. D. Silvestre; Isabel M. Marrucho. 2017. "Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings." Materials 10, no. 9: 1094.
Karen G. João; Liliana C. Tomé; Andreia S. L. Gouveia; Isabel M. Marrucho. Aqueous Biphasic Systems of Pyrrolidinium Ionic Liquids with Organic Acid-Derived Anions and K3PO4. Journal of Chemical & Engineering Data 2017, 62, 1182 -1188.
AMA StyleKaren G. João, Liliana C. Tomé, Andreia S. L. Gouveia, Isabel M. Marrucho. Aqueous Biphasic Systems of Pyrrolidinium Ionic Liquids with Organic Acid-Derived Anions and K3PO4. Journal of Chemical & Engineering Data. 2017; 62 (4):1182-1188.
Chicago/Turabian StyleKaren G. João; Liliana C. Tomé; Andreia S. L. Gouveia; Isabel M. Marrucho. 2017. "Aqueous Biphasic Systems of Pyrrolidinium Ionic Liquids with Organic Acid-Derived Anions and K3PO4." Journal of Chemical & Engineering Data 62, no. 4: 1182-1188.
This work explores ionic liquid-based membranes with siloxane functionalized cations using two different approaches: supported ionic liquid membranes (SILMs) and poly(ionic liquid)–ionic liquid (PIL–IL) composite membranes. Their CO2, CH4, and N2 permeation properties were measured at T = 293 K with a trans-membrane pressure differential of 100 kPa. The thermophysical properties of the synthesized siloxane-functionalized ILs, namely viscosity and density (data in the Supporting Information), were also determined. Contrary to what was expected, the gas permeation results show that the SILMs containing siloxane-functionalized cations have CO2 permeabilities that are lower than those of their analogues without the siloxane functionality. The addition of siloxane-based ILs into PILs increases both CO2 permeability and CO2/N2 permselectivity, although it does not significantly change the CO2/CH4 permselectivity. The prepared membranes present very diverse CO2 permeabilities, between 57 and 568 Barrer, while they show permselectivities varying from 16.8 to 36.8 for CO2/N2 and from 9.8 to 11.5 for CO2/CH4. As observed for other ILs, superior CO2 separation performances were obtained when the IL containing [C(CN)3]− is used compared to that having the [NTf2]− anion.
Liliana C. Tomé; Andreia S. L. Gouveia; Mohd A. Ab Ranii; Paul D. Lickiss; Tom Welton; Isabel M. Marrucho. Study on Gas Permeation and CO2 Separation through Ionic Liquid-Based Membranes with Siloxane-Functionalized Cations. Industrial & Engineering Chemistry Research 2017, 56, 2229 -2239.
AMA StyleLiliana C. Tomé, Andreia S. L. Gouveia, Mohd A. Ab Ranii, Paul D. Lickiss, Tom Welton, Isabel M. Marrucho. Study on Gas Permeation and CO2 Separation through Ionic Liquid-Based Membranes with Siloxane-Functionalized Cations. Industrial & Engineering Chemistry Research. 2017; 56 (8):2229-2239.
Chicago/Turabian StyleLiliana C. Tomé; Andreia S. L. Gouveia; Mohd A. Ab Ranii; Paul D. Lickiss; Tom Welton; Isabel M. Marrucho. 2017. "Study on Gas Permeation and CO2 Separation through Ionic Liquid-Based Membranes with Siloxane-Functionalized Cations." Industrial & Engineering Chemistry Research 56, no. 8: 2229-2239.
To advance the ionic liquid (IL) platform to tailor fluorinated surfactant properties, the aim of this work is to evaluate the surfactant properties of cholinium-based salts bearing perfluoroalkanoate anions. Novel surfactant ILs containing the cholinium cation [Ch]+ combined with different perfluoroalkanoate anions, namely perfluoropentanoate [PFPent]−, perfluorohexanoate [PFHex]−, perfluoroheptanoate [PFHept]−, and perfluorooctanoate [PFOct]−, were synthesized. The critical micelle concentrations (CMCs) were determined using an ionic conductivity method, at different temperatures. Thermodynamic parameters of micellization were also evaluated. The results indicate that the CMC value decreases in a linear manner with the increment of the fluoroalkyl chain length in the anion. The evaluation of the thermodynamic parameters shows that the micellization is spontaneous and entropically driven and that the enthalpy of micellization is very small. It was also observed that the introduction of the cholinium cation in these surfactants allows for smaller CMC values when compared to that of other tetraalkylammonium-based surfactants with the same fluorinated anions, in short to more efficient and green surfactants. This result is probably due to counterion association and not to counterion binding to micelle surface.
Catarina Florindo; Liliana C. Tomé; Isabel M. Marrucho. Thermodynamic Study of Aggregation of Cholinium Perfluoroalkanoate Ionic Liquids. Journal of Chemical & Engineering Data 2016, 61, 3979 -3988.
AMA StyleCatarina Florindo, Liliana C. Tomé, Isabel M. Marrucho. Thermodynamic Study of Aggregation of Cholinium Perfluoroalkanoate Ionic Liquids. Journal of Chemical & Engineering Data. 2016; 61 (12):3979-3988.
Chicago/Turabian StyleCatarina Florindo; Liliana C. Tomé; Isabel M. Marrucho. 2016. "Thermodynamic Study of Aggregation of Cholinium Perfluoroalkanoate Ionic Liquids." Journal of Chemical & Engineering Data 61, no. 12: 3979-3988.
Aiming at developing improved liquid phases for facilitated CO2 separation from post-combustion processes through supported ionic liquid membranes (SILMs), this work explores the use of binary equimolar IL mixtures containing a common imidazolium cation combined with tricyanomethane and five amino acid-based anions, glycinate, l-alaninate, taurinate, l-serinate and l-prolinate. The CO2 and N2 permeation properties of the prepared SILMs were determined at T=318.15 K and several trans-membrane pressure differentials. The results indicate that as the trans-membrane pressure differential decrease, the CO2 permeability through the SILMs containing the IL mixtures approaches or even surpasses that of the pure [C2mim][C(CN)3]. Similarly, the CO2/N2 permselectivity significantly increases, meaning that the prepared IL mixtures work as CO2 carriers under low trans-membrane pressure differentials, facilitating the flux of CO2 through SILMs. In particular, large CO2 permeabilities and high CO2/N2 permselectivities were obtained for the IL mixtures containing l-alaninate and taurinate anions, indicating that they can be considered as promising and efficient liquid phases for facilitated CO2 separation.
Andreia S.L. Gouveia; Liliana C. Tomé; Isabel M. Marrucho. Towards the potential of cyano and amino acid-based ionic liquid mixtures for facilitated CO2 transport membranes. Journal of Membrane Science 2016, 510, 174 -181.
AMA StyleAndreia S.L. Gouveia, Liliana C. Tomé, Isabel M. Marrucho. Towards the potential of cyano and amino acid-based ionic liquid mixtures for facilitated CO2 transport membranes. Journal of Membrane Science. 2016; 510 ():174-181.
Chicago/Turabian StyleAndreia S.L. Gouveia; Liliana C. Tomé; Isabel M. Marrucho. 2016. "Towards the potential of cyano and amino acid-based ionic liquid mixtures for facilitated CO2 transport membranes." Journal of Membrane Science 510, no. : 174-181.
This work explores the widening of properties of cholinium-based ionic liquids (ILs) through their combination with perfluoroalkanoate anions so that higher number of aqueous biphasic systems (ABSs) containing nontoxic cholinium-based ILs is available. For that purpose, six cholinium perfluoroalkanoate ILs were synthesized and their cytotoxicity was evaluated using three different animal cell lines, envisaging biotechnology applications. Ternary phase equilibrium data for ABSs composed of the cholinium perfluoroalkanoate, with fluoroalkyl chains from C2 up to C7, using a strong salting out agent, K3PO4, were determined at 25 °C. The results show the relevant role of the size of fluorinated alkyl chain length in the anion since, contrary to other ABSs containing ILs with increasing alkyl chain length in the anion, the ABSs with cholinium perfluoroalkanoates present well-spaced solubility curves, allowing the conclusion that these ABSs can be tuned by a proper choice of the IL. The phase splitting mechanism was also disclosed through water activity measurements.
David J. S. Patinha; Liliana C. Tomé; Catarina Florindo; Hugo R. Soares; Ana S. Coroadinha; Isabel M. Marrucho. New Low-Toxicity Cholinium-Based Ionic Liquids with Perfluoroalkanoate Anions for Aqueous Biphasic System Implementation. ACS Sustainable Chemistry & Engineering 2016, 4, 2670 -2679.
AMA StyleDavid J. S. Patinha, Liliana C. Tomé, Catarina Florindo, Hugo R. Soares, Ana S. Coroadinha, Isabel M. Marrucho. New Low-Toxicity Cholinium-Based Ionic Liquids with Perfluoroalkanoate Anions for Aqueous Biphasic System Implementation. ACS Sustainable Chemistry & Engineering. 2016; 4 (5):2670-2679.
Chicago/Turabian StyleDavid J. S. Patinha; Liliana C. Tomé; Catarina Florindo; Hugo R. Soares; Ana S. Coroadinha; Isabel M. Marrucho. 2016. "New Low-Toxicity Cholinium-Based Ionic Liquids with Perfluoroalkanoate Anions for Aqueous Biphasic System Implementation." ACS Sustainable Chemistry & Engineering 4, no. 5: 2670-2679.
This review provides a judicious assessment of the CO2 separation efficiency of membranes using ionic liquid-based materials and highlights breakthroughs and key challenges in this field.
Liliana C. Tomé; Isabel M. Marrucho. Ionic liquid-based materials: a platform to design engineered CO2 separation membranes. Chemical Society Reviews 2016, 45, 2785 -2824.
AMA StyleLiliana C. Tomé, Isabel M. Marrucho. Ionic liquid-based materials: a platform to design engineered CO2 separation membranes. Chemical Society Reviews. 2016; 45 (10):2785-2824.
Chicago/Turabian StyleLiliana C. Tomé; Isabel M. Marrucho. 2016. "Ionic liquid-based materials: a platform to design engineered CO2 separation membranes." Chemical Society Reviews 45, no. 10: 2785-2824.