Search Results (44)

Strategic utilization of carbon dioxide as both a carbon mitigation tool and a sustainable C1 feedstock represents a pivotal pathway toward green chemistry. Although poly(ionic liquid)s (PILs) exhibit promise in CO₂ conversion, conventional divinylbenzene (DVB) cross-linked architectures are limited by reduced ionic density and limited accessibility of active sites. Herein, we reported a binuclear imidazolium-functionalized PIL catalyst (P-BVIMCl), synthesized through a simple self-polymerization process, derived from rationally designed ionic liquid monomers formed by quaternization of 1,4-bis(chloromethyl)benzene with N-vinylimidazole. The dual active sites in P-BVIMCl-quaternary ammonium cation (N⁺) and nucleophilic chloride anion (Cl⁻) synergistically enhanced CO₂ adsorption/activation and epoxide ring-opening. Under optimal catalyst preparation conditions (100 °C, 24 h, water/ethanol = 1:3 (v/v), 10 wt% AIBN initiator) and reaction conditions (100 °C, 2.0 MPa CO₂, 10 mmol epichlorohydrin, 6.7 wt% catalyst loading, 3.0 h), P-BVIMCl catalyzed the synthesis of glycerol carbonate (GLC) with a yield of up to 93.4% and selectivity of 99.6%, maintaining activity close to 90% after five cycles. Systematic characterization and density functional theory (DFT) calculations confirmed the synergistic activation mechanism. This work established a paradigm for constructing high-ionic-density catalysts through molecular engineering, advancing the development of high-performance PILs for industrial CO₂ valorization. Full article

Understanding the interplay between the molecular structure of the ionic liquid (IL) subunit, the resulting nanostructure and ion transport in polymerized ionic liquids (PILs) is necessary for the realization of high-performance solid-state electrolytes required in various advanced applications. Herein, we present a detailed structural characterization of a recently synthesized series of acrylate-based PIL homopolymers and networks with imidazolium cations and chloride anions with varying alkyl spacer and terminal group lengths designed for organic solid-state batteries based on X-ray scattering. The impact of the concentrations of both the crosslinker and added tetrabutylammonium chloride (TBACl) conducting salt on the structural characteristics is also investigated. The results reveal that the length of both the spacer and terminal group influence the chain packing and, in turn, the nanophase segregation of the polar domains. Long spacers and terminal groups seem to induce denser polar aggregates sandwiched between more compact alkyl spacer and terminal group domains. However, the large inter-backbone spacing achieved seems to limit the ionic conductivity of these PILs. More importantly, our findings show that the previously reported general relationships between the ionic conductivity and the structural parameters of the nanostructure of PILs are not always attainable for different molecular structures of the IL side group. Full article

Poly(ethylene terephthalate) (PET) waste accumulation poses significant environmental challenges due to its persistent nature and current management limitations. This study explores the effectiveness of imidazolium-based neoteric solvents [Emim][OAc] and [Bmim][OAc] as catalytic co-solvents in the glycolysis of PET with ethylene glycol (EG). Reaction thermal kinetics showed that both ionic liquids (ILs) significantly enhanced the depolymerization rate of PET compared to traditional methods. The use of [Emim][OAc] offered a lower activation energy of 88.69 kJ·mol⁻¹, thus making the process more energy-efficient. The contribution of key process parameters, including temperature (T), plastic-to-ionic liquid (P/IL) mass ratio, and plastic-to-solvent (P/S) mass ratio, were evaluated by means of a factorial analysis and optimized to achieve the maximum PET conversion for both neoteric solvents. The relevance sequence for both ionic liquids involved the linear factors T and P/S, followed by the interaction factors T×P/S and T×P/IL, with P/IL being the less significant parameter. The optimal conditions, with a predicted conversion of 100%, involved a temperature of 190 °C, with a P/IL of 1:1 and a P/S of 1:2.5, regardless of the IL used as the catalytic co-solvent. Full article

The escalating emissions of CO₂ into the atmosphere require the urgent development of technologies aimed at mitigating environmental impacts. Among these, aqueous amine solutions and polymeric membranes, such as cellulose acetate and polyimide are commercial technologies requiring improvement or substitution to enhance the economic and energetic efficiency of CO₂ separation processes. Ionic liquids and poly(ionic liquids) (PILs) are candidates to replace conventional CO₂ separation technologies. PILs are a class of materials capable of combining the favorable gas affinity exhibited by ionic liquids (ILs) with the processability inherent in polymeric materials. In this context, the synthesis of the IL GLYMIM[Cl] was performed, followed by ion exchange processes to achieve GLYMIM variants with diverse counter anions (NTf₂⁻, PF₆⁻, and BF₄). Subsequently, PIL membranes were fabricated from these tailored ILs and subjected to characterization, employing techniques such as SEC, FTIR, DSC, TGA, DMA, FEG-SEM, and CO₂ sorption analysis using the pressure decay method. Furthermore, permeability and ideal selectivity assessments of CO₂/CH₄ mixture were performed to derive the diffusion and solubility coefficients for both CO₂ and CH₄. PIL membranes exhibited adequate thermal and mechanical properties. The PIL-BF₄ demonstrated CO₂ sorption capacities of 33.5 mg CO₂/g at 1 bar and 104.8 mg CO₂/g at 10 bar. Furthermore, the PIL-BF₄ membrane exhibited permeability and ideal (CO₂/CH₄) selectivity values of 41 barrer and 44, respectively, surpassing those of a commercial cellulose acetate membrane as reported in the existing literature. This study underscores the potential of PIL-based membranes as promising candidates for enhanced CO₂ capture technologies. Full article

Repairing damaged tissue caused by bacterial infection poses a significant challenge. Traditional antibacterial hydrogels typically incorporate various components such as metal antimicrobials, inorganic antimicrobials, organic antimicrobials, and more. However, drawbacks such as the emergence of multi-drug resistance to antibiotics, the low antibacterial efficacy of natural agents, and the potential cytotoxicity associated with metal antibacterial nanoparticles in hydrogels hindered their broader clinical application. In this study, we successfully developed imidazolium poly(ionic liquids) (PILs) polymer microspheres (APMs) through emulsion polymerization. These APMs exhibited notable antibacterial effectiveness and demonstrated minimal cell toxicity. Subsequently, we integrated the APMs into a gelatin methacryloyl (GelMA)—polyethylene glycol (PEG) hydrogel. This composite hydrogel not only showcased strong antibacterial and anti-inflammatory properties but also facilitated the migration of human skin fibroblasts (HSF) and human umbilical vein endothelial cells (HUVECs) and promoted osteogenic differentiation in vitro. Full article

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young’s modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10⁻⁶ S·cm⁻¹ at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10⁻⁵ S·cm⁻¹ and further increases to 10⁻³ S·cm⁻¹ in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries. Full article

In recent years, the issue related to electronic waste production has been gaining prominence. One of the approaches considered to limit the impact of e-waste on the environment involves the development of biodegradable electronic devices or devices that dissolve in the environment at the end of their life cycle. In this study, we present the preliminary results related to the creation of a sensor that could meet both criteria. The device was constructed using a composite material obtained by impregnating a membrane of polycaprolactone (a biodegradable polymer) with 1-Ethyl-3-Methylimidazolium tetrafluoroborate (a water-soluble ionic liquid), which was coated with a conductive silver-based varnish. Leveraging the piezoionic effect, the device has been proven to function as a vibration sensor with a sensitivity of approximately 1.9 × 10⁻⁵ V/mm and a resolution of about 0.15 mm. Full article

Hexaethylene glycolic vinyl imidazolium (hexaEGVIM) was supported on N-vinyl caprolactam via covalent bonds through simple copolymerization to form poly caprolactam-supported hexaethylene glycol-substituted imidazolium salts (PCLS-hexaEGIM). The resulting heterogeneous PCLS-hexaEGIM promoter was active, selective, and stable for aliphatic nucleophilic substitution reactions using alkali metal salts. The alkali metal salts dramatically enhanced the reactivity of this heterogeneous catalyst with easily isolable higher product yields, reducing the formation of by-products. Therefore, nucleophilic fluorination and other substitution reactions can act as highly efficient catalysts in various sulfonyloxyalkanes and haloalkanes with regard to their corresponding fluorinated products. Full article

In this study, we set out to modify poly(lactic acid) (PLA) by incorporating epoxidized ionic liquids (ILs) that were specifically designed with imidazolium-NTf₂ moieties. First, we synthesized di-, tri- and tetra-epoxidized ILs, which were incorporated into a PLA matrix at 3, 5, and 10 wt% through a melt extrusion process. We investigated the relationship between the structure and properties of the resulting materials in terms of thermal, mechanical, rheological, and surface properties. The results showed the potential of ILs to impact these properties. Notably, the tri- and tetra-epoxidized ILs enhanced the thermal stability of the PLA matrix as well as the crystallinity while reducing the glass transition temperature and melting point, which is promising for reactive extrusion processing. Overall, this research opens new routes for using reactive ILs to improve the processing and properties of PLA polymers. Full article

Poly(ethylene oxide) (PEO)-based copolymers are at the forefront of advanced membrane materials for selective CO₂ separation. In this work, free-standing composite membranes were prepared by blending imidazolium-based ionic liquids (ILs) having different structural characteristics with a PEO-based copolymer previously developed by our group, targeting CO₂ permeability improvement and effective CO₂/gas separation. The effect of IL loading (30 and 40 wt%), alkyl chain length of the imidazolium cation (ethyl- and hexyl- chain) and the nature of the anion (TFSI^-, C(CN)₃^-) on physicochemical and gas transport properties were studied. Among all composite membranes, PEO-based copolymer with 40 wt% IL3-[HMIM][TFSI] containing the longer alkyl chain of the cation and TFSI^- as the anion exhibited the highest CO₂ permeability of 46.1 Barrer and ideal CO₂/H₂ and CO₂/CH₄ selectivities of 5.6 and 39.0, respectively, at 30 °C. In addition, almost all composite membranes surpassed the upper bound limit for CO₂/H₂ separation. The above membrane showed the highest water vapor permeability value of 50,000 Barrer under both wet and dry conditions and a corresponding H₂O/CO₂ ideal selectivity value of 1080; values that are comparable with those reported for other highly water-selective PEO-based polymers. These results suggest the potential application of this membrane in hydrogen purification and dehydration of CO₂ gas streams. Full article

In the current study, we have synthesized an imidazolium based cross-linked polymer, namely, 1-vinyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide (poly[veim][Tf₂N]-TRIM) using trimethylolpropane trimethacrylate as cross linker, and demonstrated its efficiency for the removal of two extensively used ionic dyes—methylene blue and orange-II—from aqueous systems. The detailed characterization of the synthesized poly[veim][Tf₂N]-TRIM was performed with the help of ¹H NMR, TGA, FT-IR and FE-SEM analysis. The concentration of dyes in aqueous samples before and after the adsorption process was measured using an UV-vis spectrophotometer. The process parameters were optimised, and highest adsorption was obtained at a solution pH of 7.0, adsorbent dosage of 0.75 g/L, contact time of 7 h and dye concentrations of 100 mg/L and 5.0 mg/L for methylene blue and orange-II, respectively. The adsorption kinetics for orange-II and methylene blue were well described by pseudo-first-order and pseudo–second-order models, respectively. Meanwhile, the process of adsorption was best depicted by Langmuir isotherms for both the dyes. The highest monolayer adsorption capacities for methylene blue and orange-II were found to be 1212 mg/g and 126 mg/g, respectively. Overall, the synthesized cross-linked poly[veim][Tf₂N]-TRIM effectively removed the selected ionic dyes from aqueous samples and provided >90% of adsorption efficiency after four cycles of adsorption. A possible adsorption mechanism between the synthesised polymeric adsorbent and proposed dyes is presented. It is further suggested that the proposed ionic liquid polymer adsorbent could effectively remove other ionic dyes and pollutants from contaminated aqueous systems. Full article

Wounds, particularly under low-hydration conditions, require more time to repair successfully. Therefore, there is an urgent need to develop wound dressings that can accelerate wound healing. Hydrogels, which can maintain a moist environment around the wound and allow gas to pass through the material, act as antibacterial hydrogels as dressings and have great application value in the treatment of wounds. In addition, wound dressings (hydrogels) containing antibacterial capacity have lasting antibacterial effects and reduce damage to cells. In this work, we firstly synthesized two antibacterial agents: imidazolium poly(ionic liquids) containing sulfhydryl (Imidazole-SH) and ε-Poly(lysine) containing SH (EPL-SH). Then, lysine as a cross-linking agent, by “thiol-ene” click reaction, was mixed with Deferoxamine (DFO) to prepare the antibacterial hydrogels. The in vitro assays showed that the hydrogels could effectively kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). In addition, it also could reduce the inflammatory response produced by Lipopolysaccharide (LPS). More importantly, according to the transwell and angiogenesis assays, DFO-incorporated hydrogels promoted the migration and vascular repair of human umbilical vein endothelial cells (HUVECs). All the results revealed that the hydrogels provided new strategies for wound dressings. Full article

Two sets of four different supported catalyst materials were prepared. One set was obtained by polymerization of a bis-vinylimidazolium salt, which formed a poly(ionic liquid) coating on SiO₂, TiO₂, boron nitride BN, and carbon nitride C₃N₄. The other set was, instead, obtained by immobilizing Keggin heteropolyacid H₃PW₁₂O₄₀ onto poly-imidazolium functionalized materials. All the catalysts, including the bare supports, were subjected to physical and chemical characterization by XRD, SEM, Specific Surface Area and pore size measurements, TGA, FTIR, and acidity-basicity measurements. The catalytic activity of the materials was tested versus the fructose dehydration in water solution at two different sugar initial concentrations (0.3 and 1 M). Tests lasted 3 h with an amount of catalyst of 2 g∙L⁻¹. The presence of the poly-imidazolium on the surface of the supports increased the catalytic conversion of fructose to 5-hydroxymethylfurfural (the most abundant compound obtained) and was further improved by the contemporary presence of the heteropolyacid, at least for the highest initial fructose concentration. In the latter conditions, the highest yield of 5-hydroxymethylfurfural (>40%) was also obtained. Full article

In this work, ionic liquid (IL)-cured epoxy resins were modified by adding poly(ε-caprolactone) (PCL). Three different ILs were used in order to study how (a) the chemical structure of the ILs and (b) the PCL content affect the phase behaviour, microstructure, mechanical and adhesive properties. Regardless of the IL used or the PCL content, the obtained materials showed a single phase. The addition of PCL to the epoxy resin resulted in plasticizing of the network blends, lower glass transition temperatures (T_g), and crosslinking densities (ν_e). Low PCL contents did not have a significant impact on the mechanical properties. However, the adhesive properties improved significantly at low PCL contents. Higher PCL contents led to a significant increase in toughness, especially in the case of the imidazolium-based IL. The balance achieved between the mechanical and adhesive properties of these IL-cured epoxy/PCL blends constitutes an important step towards sustainability. This is because a biodegradable polymer (PCL) was used to substitute part of the epoxy resin, and the ILs—which are non-volatile and cure effectively at much lower contents—were used instead of conventional curing agents. Given the wide use of this kind of materials in the adhesive industry, the practical significance of these results must be emphasised. Full article

Charge transport, diffusion properties, and glassy dynamics of blends of imidazolium-based ionic liquid (IL) and the corresponding polymer (polyIL) were examined by Pulsed-Field-Gradient Nuclear Magnetic Resonance (PFG-NMR) and rheology coupled with broadband dielectric spectroscopy (rheo-BDS). We found that the mechanical storage modulus $\left(G^{\prime }\right)$ increases with an increasing amount of polyIL and $G^{\prime }$ is a factor of 10,000 higher for the polyIL compared to the monomer ($G_{IL}^{\prime }$= $7.5$ Pa at 100 rad s⁻¹ and 298 K). Furthermore, the ionic conductivity $\left({\sigma }_0\right)$ of the IL is a factor $1000$ higher than its value for the polymerized monomer with $3.4\times {10}^{-4}$ S cm⁻¹ at $298$ K. Additionally, we found the Haven Ratio ($H_R)$ obtained through PFG-NMR and BDS measurements to be constant around a value of $1.4$ for the IL and blends with 30 wt% and 70 wt% polyIL. These results show that blending of the components does not have a strong impact on the charge transport compared to the charge transport in the pure IL at room temperature, but blending results in substantial modifications of the mechanical properties. Furthermore, it is highlighted that the increase in ${\sigma }_0$ might be attributed to the addition of a more mobile phase, which also possibly reduces ion-ion correlations in the polyIL. Full article