Search Results (185)

1-Butyl-3-methylimidazolium (bmim) ionic liquids (ILs) are widely used for lignocellulose fractionation, yet their role extends beyond mere solvents. This study revealed that bmim-based ILs act as active chemical reagents, modifying the lignin structure in an anion-dependent manner. Thermal treatment (80–150 °C) of spruce dioxane lignin with [bmim]OAc, [bmim]Cl, and [bmim]MeSO₄ resulted in two distinct transformation pathways. In [bmim]MeSO₄, acidic catalysis dominates, leading to lignin condensation (increase in weight-average molecular weight, M_w, to 15.2 kDa at 150 °C) and intense sulfur incorporation (up to 9.9%) via anion-derived methylation/sulfation. Conversely, [bmim]OAc promotes depolymerization (decrease in M_w to 3.6 kDa) and efficient covalent bonding of the bmim cation to lignin (up to 10.8 cations per 100 aromatic units and a 6.5% nitrogen content at 150 °C), preventing condensation. Two-dimensional NMR and HPLC-HRMS analyses revealed the formation of a C–C bond between the C₂ atom of the imidazole ring and the α-carbon of the phenylpropane lignin fragments and allowed for the identification of a number of individual nitrogen-containing lignin oligomers in the [bmim]OAc-treated samples. Their formation likely proceeds via nucleophilic addition of the N-heterocyclic carbene (NHC), derived from the bmim cation by deprotonation with the highly basic acetate anion, to aldehyde groups. The action of [bmim]Cl primarily induces acid-catalyzed transformations of lignin with minimal covalent modification. These findings redefine imidazolium ILs as reactive media in biorefining, where their covalent interactions can influence the properties of lignin but complicate its native structure and the recyclability of the IL. Full article

Understanding the interactions between ionic liquid ions and lithium-metal surfaces is critical for designing safer and more efficient lithium metal batteries. In this work, we use density functional theory to investigate the electronic structure, binding energies, work-function shifts and interfacial charge redistribution of several ionic liquid ions, including FSI⁻, TFSI⁻, ${\mathrm{P}\mathrm{F}}_6^{-}$, ${\mathrm{B}\mathrm{F}}_4^{-}$, DFOB⁻, Pyr14⁺, and EMIM⁺, on a Li-metal anode (Li_m). Absorption orientation-dependent effects are examined for each molecule. Specifically, differences in charge density and electron localization function analyses revealed unique patterns of electron accumulation and delocalization that highlighted specific atomic roles in interfacial bonding. Interfacial charge transfer is analyzed through Bader charges, revealing a moderate charge redistribution for the cations (EMIM⁺, Pyr14⁺), and a more significant charge uptake for the reactive anions (FSI⁻, TFSI⁻, DFOB⁻). Among cations, EMIM⁺ was determined to have the most interfacial stability, while Pyr14⁺ displayed mid-level reactivity. For the anions, varying tendencies for bond formation with lithium metal and potential fragmentation could be determined. Overall, these discoveries detail an atomistic analysis of ionic liquid to Li_m interactions providing additional pathways for molecular design techniques to stabilize electrolytes performing not high-cost computational calculations. Full article

This study investigates the interfacial behavior of four phosphate ester ionic liquids (ILs) with contrasting cation hydrophobicity under humid environments. Through tribological tests, surface analysis, and molecular dynamics simulations, we reveal how moisture absorption governs lubricant film organization at metal interfaces. Aromatic ILs (imidazolium/pyridinium cations) exhibit significant degradation in lubrication after moisture exposure, with friction coefficients increasing by 0.03–0.05 and wear volumes scaling with humidity. This deterioration arises from competitive water–cation adsorption, where hydrogen bonding disrupts Fe-cation coordination bonds and destabilizes the protective film. In contrast, aliphatic ILs (tetraalkylammonium/phosphonium cations) maintain robust tribological performance. Their alkyl chains spatially confine water to outer adsorption layers (>17 Å from the surface), preserving a stable core lubricating film (~14 Å thick). Molecular dynamics simulations confirm that water co-adsorbs with aromatic cations (RDF peak: 2.5 Å), weakening interfacial interactions, while aliphatic ILs minimize cation–water affinity (RDF peak: 4 Å). These findings establish cation hydrophobicity as a critical design parameter for humidity-resistant lubricants, providing fundamental insights into water-mediated interfacial phenomena in complex fluid systems. Full article

Machine learning models and web-based tools have been developed for predicting key properties of imidazolium-based ionic liquids. Two high-quality datasets containing experimental density and viscosity values at 298 K were curated from the ILThermo database: one containing 434 systems for density and another with 293 systems for viscosity. Molecular structures were optimized using the GOAT procedure at the GFN-FF level to ensure chemically realistic geometries, and a diverse set of molecular descriptors, including electronic, topological, geometric, and thermodynamic properties, was calculated. Three support vector regression models were built: two for density (IonIL-IM-D1 and IonIL-IM-D2) and one for viscosity (IonIL-IM-V). IonIL-IM-D1 uses three simple descriptors, IonIL-IM-D2 improves accuracy with seven, and IonIL-IM-V employs nine descriptors, including DFT-based features. These models, designed to predict the mentioned properties at room temperature (298 K), are implemented as interactive applications on the atomistica.online platform, enabling property prediction without coding or retraining. The platform also includes a structure generator and searchable databases of optimized structures and descriptors. All tools and datasets are freely available for academic use via the official web site of the atomistica.online platform, supporting open science and data-driven research in molecular design. Full article

A theoretical study was performed using Density Functional Theory (DFT) to investigate the impact of π-conjugated aliphatic chain growth on the chemical and electronic properties of hybrid antimony pentachloride salts with pyridine- and imidazolium-based cations. Ten molecular systems were optimized to determine their ground-state geometry. Using conceptual DFT, parameters such as chemical hardness, electrophilicity index, electroaccepting power, and electrodonating power were studied. The energy gap was obtained for all ten molecular systems, ranging from −4.038 to −3.706 eV as the chain length increased, favoring intramolecular charge transfer in long-chain systems. Natural bond orbital (NBO) analysis showed charge redistribution between anion and cation as the π-conjugated aliphatic chain grows. At the same time, non-covalent interaction (NCI) studies revealed key attractions and repulsive interactions, such as H···Cl and Cl···π, which are modulated by chain length. These results demonstrate that the structural modification of the cation allows for the fine-tuning of the electronic properties of ionic liquids (ILs). Increasing the conjugated aliphatic chain length was observed to reduce the chemical hardness and electrophilicity index, as well as affecting the Egap of the molecular systems. This work demonstrates that there is an optimal size for the inorganic ion, allowing it to form an optimal IL compound. Full article

Hydrofluorocarbons (HFC) are today widely used as refrigerants, solvents, or aerosols for fire protection. Due to their non-negligible environmental impact, there exists an increasing interest towards their effective separation and recovery, which still remains a major challenge. This work presents a comprehensive thermodynamic and transport modeling approach able to describe HFC sorption and transport in different amorphous polymers, including glassy, rubbery, and copolymers, as well as in supported Ionic Liquid membranes (SILMs). In particular, the literature solubility data for refrigerants such as R-32, R-125, R-134a, and R-152a is analyzed by means of the Sanchez–Lacombe Equation of State (SL-EoS), and its non-equilibrium extension (NELF), to predict gas uptake in complex polymeric materials. The Standard Transport Model (STM) is then employed to describe permeability behaviors, incorporating concentration-dependent diffusion using a mobility coefficient and thermodynamic factor. Results demonstrate that fluorinated gases exhibit strong affinity to fluorinated and high free-volume polymers, and that solubility is primarily governed by gas condensability, molecular size, and polymer structure. The combined EoS–STM approach accurately predicts both solubility and permeability across different pressures in all polymers, including SILM. The thorough study of HFC transport in polymer membranes provided both systematic insights and predictive capabilities to guide the design of next-generation materials for refrigerant recovery and low-GWP separation processes. Full article

To examine how reaction media influence the copolymerization processes of acrylamide-based copolymers, [BMIM]Oac and water were utilized as the reaction media. Four copolymers P(AM-SSS) (H₂O), P(AM-UA) (H₂O), P(AM-SSS) (ILs), and P(AM-UA) (ILs) were synthesized using the soluble monomer sodium p-styrene sulfonate (SSS), the insoluble monomer 10-undecylenoic acid (UA), and acrylamide (AM). The properties of the copolymers were characterized using infrared spectroscopy and ¹H NMR, and the copolymerization rates of the monomers and the segment sequences of the copolymers were calculated. The results indicated that copolymerization of SSS in ionic liquids could reduce the length of the continuous units of AM in the copolymer’s molecular chain from 231.2866 to 91.1179, with a more uniform distribution within the molecular chain. The thermal stability and micro-morphology of the copolymers were tested using a synchronous thermal analyzer and scanning electron microscopy, and the resistance of the copolymer solutions to temperature, salt, and shear were evaluated. Comparisons revealed that the three-dimensional spatial structure formed by the copolymers in ionic liquids is robust and loose. When AM and SSS polymerize in [BMIM]Oac, the resulting copolymer exhibits a higher viscosity retention rate in temperature and shear resistance tests, with a thermal decomposition temperature reaching 260 °C. Conversely, when AM and UA polymerize in [BMIM]Oac, the copolymer demonstrates good salt resistance, maintaining a viscosity retention rate of 259.04% at a Na⁺ concentration of 200,000 mg/L. Therefore, the ionic liquid [BMIM]Oac can enhance the various application performances of copolymers formed by monomers with different solubilities and AM. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) into value-added multi-carbon C₂₊ products holds significant promise for sustainable chemical synthesis and carbon-neutral energy cycles. Among the various strategies developed to enhance CO₂RR, the use of ionic liquids (ILs) has emerged as a powerful approach for modulating the local microenvironment and electronic structure of Cu-based metal catalysts. In this study, to unravel the molecular-level mechanisms underlying these enhancements, density functional theory calculations (DFTs) were employed to systematically explore how ILs with different terminal groups modulate the electronic reconstruction of the Cu surface, further affecting the *CO–*CO coupling and product selectivity. Electronic structure analyses reveal that ILs bearing polar moieties (–SH, –COOH) can synergistically enhance the interfacial electron accumulation and induce an upshift of the Cu d-band center, thereby strengthening *CO adsorption. In contrast, nonpolar IL (CH₃) exhibits negligible effects, underscoring the pivotal role of ILs’ polarity in catalyst surface-state engineering. The free energy diagrams and transition state analyses reveal that ILs with polar groups significantly lower both the reaction-free energy and activation barrier associated with the *CO–*CO coupling step. This energetic favorability selectively inhibits the C₁ product pathways and hydrogen evolution reaction (HER), further improving the selectivity of C₂ products. These theoretical insights not only unveil the mechanistic origins of IL-induced performance enhancement but also offer predictive guidance for the rational design of advanced IL–catalyst systems for efficient CO₂ electroreduction. Full article

Bacterial cellulose (BC) is a highly pure and crystalline cellulose produced via bacterial fermentation. However, due to its chemical structure made of strong hydrogen bonds and its high molecular weight, BC can neither be melted nor dissolved by common solvents. Therefore, processing BC implies the use of very strong, often toxic and dangerous chemicals. In this study, we proved a green method to produce electrospun BC fibers by testing different ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium acetate (BmimAc), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium dicyanamide (EmimDCA), either individually or as binary mixtures. Moreover, γ-valerolactone (GVL) was tested as a co-solvent derived from renewable sources to replace dimethyl sulfoxide (DMSO), aimed at making the viscosity of the cellulose solutions suitable for electrospinning. A BmimAc and BmimAc/EmimTFSI (1:1 w/w) mixture could dissolve BC up to 3 w%. GVL was successfully applied in combination with BmimAc as an alternative to DMSO. By optimizing the electrospinning parameters, meshes of continuous BC fibers, with average diameters ~0.5 μm, were produced, showing well-defined pore structures and higher water absorption capacity than pristine BC. The results demonstrated that BC could be dissolved and electrospun via a BmimAc/GVL solvent system, obtaining ultrafine fibers with defined morphology, thus suggesting possible greener methods for cellulose processing. Full article

This work aims to assess the intermolecular interaction of choline ionic liquids (ILs) (choline malonate ([Ch][Mal]), choline succinate ([Ch][Suc]), and choline valinate ([Ch][Val]) with two enzymes (lysozyme and α-chymotrypsin). We evaluated the state of the tertiary protein structure using circular dichroism (CD) spectrometry and quantified the binding parameters of the binding of the ionic liquids to the enzymes by fluorescence spectroscopy. The binding energies of the enzymes and the localization of ions on them were estimated using the molecular docking. We then analyzed the relationship between the enzymes’ thermostability and their tendency towards aggregation in the enzyme/ionic liquid systems. The obtained results were compared with previous data on albumins to identify similarities and differences between the behavior of enzymes and albumins in ionic liquid solutions. Despite the comparable values of the binding constants, the effect of ionic liquids on the thermostability of enzymes was the opposite of their effect on albumins. In addition, although these ionic liquids promoted aggregation in both enzymes and albumins, this effect was much more pronounced for albumins. Full article

In this study, the chemically supported ionic liquids (CSILs) were synthesized by ultrasound irradiation (UI) to improve the preparation process and further strengthen the adsorption performance of CSILs towards vanadium (V). The impacts of UI and conventional mechanic stirring (CMS) on the synthesis and adsorption characteristics of polystyrene [1-butyl-3-methylimidazolium][nitrate] (PS[C₄mim][NO₃]) were comparatively investigated. The experimental results demonstrate that ultrasound can dramatically shorten the preparation time from 1920 min to 15 min, and HNO₃ dosage is reduced by 15.79%. Under the same adsorption conditions, the CSILs synthesized by UI achieve the maximal adsorption capacity towards vanadium (V) as 248.95 mg/g at 150 min, while the CSILs processed by CMS reach 223.90 mg/g at 105 min. Particularly, the adsorption capacity of CSILs synthesized by UI can be maintained as 96.42% of the initial value after 10 cycles of adsorption–desorption, while that of CSILs processed by CMS maintain as 94.87%. The adsorption isotherm and kinetics fitting demonstrate that vanadium (V) adsorption by two CSILs is dominated by chemisorption as a single molecular layer. Additionally, the adsorption reaction of vanadium (V) by these two CSILs are both endothermic, and entropy increases. Fourier transform infrared, scanning electron microscopy, and energy spectrometry analyses prove that PS[C₄mim][NO₃] is successfully prepared by UI and CMS methods, and ultrasound waves will not destroy the intact spherical structure of the support resins. The current work provides a novel insight for the efficient synthesis of CSILs, which is also a potential technique for improving the adsorption performance of the adsorbents towards valuable metals. Full article

With the rapid global increase in the use of digital devices and electric vehicles, solid polymer electrolytes (SPEs) have emerged as promising candidates for all-solid-state batteries. They are expected to resolve safety concerns and overcome the limitations of energy density and charging speed associated with traditional Li-ion batteries with liquid electrolytes. However, a limited understanding of ionic conduction mechanisms remains a significant barrier to their further development and practical application. In this study, we employed molecular dynamics simulations using the COMPASS II force field under NPT/NVT ensembles at 298 K to investigate the static and dynamic properties of poly(ethylene carbonate) (PEC) electrolytes at various salt concentrations. Key analyses included the radial distribution function, solvation free energy, and mean-square displacement (MSD) of individual Li cations. Based on their MSD data, Li cations were categorized into “faster” or “slower” groups, corresponding to conductivity levels above or below the average in each model. Our findings reveal that, at higher concentrations, a smaller fraction of faster Li cations contributes disproportionately more than slower Li cations to the overall mobility, highlighting that targeted manipulation of solvation structures could enhance ion transport efficiency in highly concentrated SPEs. Additionally, changes in coordination number and solvation free energy for both faster and slower Li cations suggest the existence of three different solvation patterns as salt concentration increases. These insights provide a deeper understanding of ionic transport and solvation structures in PEC electrolytes, with potential implications for the design of more efficient all-solid-state batteries. Full article

As a kind of bioactive component in the rhizome of natural plant Curcuma longa L. (turmeric), curcumin is almost insoluble in water at neutral and acidic pH, which limits its further utilization and development. At the same time, traditional extraction and separation processes typically require the use of a large number of organic solvents. Ionic liquids (ILs) are organic molten salts with melting points below 100 °C. When an ionic liquid exists in a liquid state at or near room temperature, it is referred to as a room-temperature ionic liquid (RTIL). They have a temperature range, good physical and chemical stability, and good structural designability. They have a strong solubilization enhancement effect for many organic compounds. This study first explored the molecular forms of curcumin in ionic liquid aqueous solutions and the intermolecular interactions between curcumin and ionic liquids using spectral analysis and computational chemistry methods; furthermore, using an ionic liquid aqueous solution as an extraction agent, curcumin-like substances (curcuminoids) were extracted from turmeric powders under ultrasound assisted conditions, revealing the relationship between the structure of the ionic liquid and the extraction efficiency. After that, a kinetic study was conducted for the extraction of curcuminoids from turmeric powders, using second-order kinetics fitting to obtain the rate constant and initial extraction rate during the extraction process. Finally, the comparison with a ComplexGAPI tool and antioxidant experiment was performed on the extraction by using ionic liquids and traditional solvent. The full results can provide reference for the design of IL extractants and their application for natural products. 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

We report the synthesis and characterization of a novel asymmetric imidazolium-based ionic liquid crystal (ILC) dimer exhibiting stable smectic phases over a wide temperature range, including room temperature. This unique molecular structure, combining two distinct mesogenic cores, reduces packing density, which enhances ion mobility and achieves high ionic conductivity in the smectic phase (0.1 mS cm⁻¹ at 40 °C). Electrochemical impedance spectroscopy (EIS) confirmed improved ionic conductivity at lower temperatures, along with a stable electrochemical window of ±3 V. Application as a solid-state electrolyte in an electrochromic device demonstrated effective switching behavior and reversible redox cycles. These findings suggest that this asymmetric imidazolium-based ILC is a viable candidate for advanced electrochemical applications due to its structural stability and anisotropic ionic pathways. Full article