Ionic Liquid Media Research Articles

Deciphering the Coarse-Grained Model of Ionic Liquid by Tunning the Interaction Level and Bead Types of Martini 3 Force Field

In recent years, ionic liquids (ILs) have served as potential solvents to dissolve organic, inorganic, and polymer materials. A copolymer (for example, Pluronic) can undergo self-organization by forming a micelle-like structure in pure IL medium, and its assembly depends upon the composition of IL. To evaluate the role of ILs, accurate coarse-grained (CG) modeling of IL is needed. Here, we modeled 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]) ionic liquid (IL) using a CG framework. We optimized CG parameters for the [DCA]− anion by tuning the non-bonded parameters and selecting different kinds of beads. The molecular density (ρ) and radial distribution function (RDF) of our CG model reveal a good agreement with the all-atom (AA) simulation data. We further validated our model by choosing another imidazolium-based cation. Our modified CG model for the anion shows compatibility with the cation and the obtained density matches well with the experimental data. The strategies for developing the CG model will provide a guideline for accurate modeling of new types of ILs. Our CG model will be useful in studying the micellization of non-ionic Pluronic in the [EMIM][DCA] IL medium.

Ionic liquid [TEMPOLQ8][HSO4] as oxidant cum solvent and catalyst for metal free tandem oxidative synthesis of quinazolin-4(3H)-ones

A new ionic liquid (IL), TEMPO-oxyoctylquinolinium hydrogen sulfate i.e., [TEMPOLQ8][HSO4] has been designed and reported for the first time as an efficient oxidant cum catalyst and solvent for one pot oxidative synthesis of quinazolin-4(3H)-ones from anthranilamide and benzyl alcohols. The reactions proceed to completion giving selectively quinazolin-4(3H)-ones in 6 hours at 120 °C eliminating the need for any external oxidant or transition metal catalysts. [TEMPOLQ8][HSO4] worked as an efficient catalyst cum oxidant and solvent for the oxidation of benzyl alcohols to benzaldehydes at 80 °C for 6 hours. This is the first report of controlled oxidation of benzyl alcohols to benzaldehydes under ionic liquid media in the absence of any external oxidant or catalyst. The in-situ generated aldehyde then couples with anthranilamide to afford the product. The protocol covers a wide substrate scope with access to potent medicinal drugs. Moreover, three gram-scale syntheses provide the synthetic utility of the protocol. The catalytic procedure was developed with green chemistry principles and its eco-friendliness was confirmed by its high eco-scale values. The IL was found to be more efficient compared to seven other newly synthesized ionic liquids used in the work.

A novel experimental approach for the catalytic conversion of lignocellulosic Bambusa bambos to bioethanol

Bambusa bambos (B.B) biomass is cellulose rich lignocellulosic material, containing 47.49% cellulose, 17.49% hemicellulose, 23.56% lignin was used as a potential substrate for bioethanol production. The research paper investigates the use of B.B biomass as a substrate for bio-ethanol production through a two-phase catalytic conversion process. Four water-regulated regimes were identified to optimize the conversion of lignocellulosic biomass to biofuel precursors. The catalytic hydrolysis of B.B using CuCl2 was conducted for 10 hours at 110˚C, in aprotic ionic liquid (1-Butyl-3-methylimidazolium chloride) medium. The concentrations of glucose and 5-hydroxymethylfurfural (5-HMF) were measured while varying the amount of water addition. Water played a crucial role in the conversion of cellulose to glucose and 5-HMF by influencing product yields through the interplay of transport properties like heat conduction and viscosity. The highest glucose yield was achieved at 60.82% when operating at a water inclusion rate of 115.72 µL water/h for a duration of 6 hours at 110˚C. On the other hand, the maximum HMF yield was observed as 5.84% at water inclusion rate of 77.15 µL water/h for 5 hours at 110˚C. Yeast mediated glucose fermentation resulted in a bioethanol concentration of 5.5 mg/mL utilizing 15 mg/mL of catalytically produced glucose at a temperature of 30°C. After catalytic hydrolysis, the ionic liquid was also efficiently recycled for a sustainable economy.

Extractive Mass Transfer of Zr(IV) into a Hydrophobic Ionic Liquid Medium Containing Diglycolamide Extractant: Solvent Extraction and Spectroscopic Analysis.

Solvent extraction of Zr(IV) in ionic liquid (IL) medium is less known and Zr(IV) - IL chemistry indeed needs exploration to realize the coordination approach of Zr(IV) in IL phase. In view of this, in the present work, a strongly hydrophobic imidazolium based IL: 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) as the medium containing a diglycolamide (DGA) extractant: N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) was opted to understand the extraction behavior of Zr(IV) from nitric acid medium. Different experimental parameters such as the concentration of initial nitric acid, initial feed metal concentration, equilibration time and ligand concentration were tuned to unravel the extraction efficiency of the proposed IL phase towards Zr(IV). The extraction scenario was completely dependent on the hydrophobicity of IL diluent and increasing extraction trend with an increase in feed acidity along with the coordination of two TODGA molecules ensured Zr(IV) - complex formation in a neutral solvation mechanistic pathway. The extraction trend of Zr(IV) was compared with molecular diluent (n-dodecane (n-DD)) containing TODGA and a phase modifier: N,N-dihexyloctanamide (DHOA). The coordination aspect of Zr(IV) with ligand in IL phase was ascertained spectroscopically to validate Zr(IV) loading in IL phase. Thermodynamics of Zr(IV) extraction revealed the nature of the extraction process and the complex formation.

Photochromic ionogel with a wide temperature range and fatigue resistance for high-resolution rewritable information record

Recently, photochromic hydrogels have received significant attention and hold substantial promise for rewritable information record. However, the intrinsic instability of hydrogels has restricted their applications. Herein, a photochromic ionogel aiming at extending service life for long-term use is presented by embedding photochromic ammonium molybdate tetrahydrate [(NH4)6Mo7O24·4H2O] (Mo7) in engineered double networks. Covalently cross-linked 2-hydroxyethyl acrylate (HEA) and self-assembled cationic cellulose (JR-400) constitute the networks, and a protic ionic liquid of ethylammonium nitrate (EAN) is immobilized therein. Such a design affords the ionogel comprehensive properties, including high optical transparency (>97%), good adhesion, anti-dehydration, wide operating temperature range (–60 to 150 °C) as well as the sensitive and stable UV-light responsiveness (within 30 s). Besides, the ionogel exhibits admirable mechanical properties of high toughness (over 180 kJ/m3), excellent resilience and a high fatigue threshold (over 1000 cycles with negligible hysteresis). The photochromic process is typically accomplished by photoreduction of Mo7, which is combined with network through electrostatic interaction with quaternized JR-400. The distinctive feature is that EAN serving as both proton donor and electron donor, plays a dominant role in coloration process and formation of charge-transfer complex. The photochromic mechanism which is less well understood in ionic liquid medium, has been revealed. Remarkably, the ionogel used as an information carrier exhibits outstanding stability in a wide operating temperature range. The superiorities of the photochromic ionogel including accurate information recording capacity and application in harsh environments have greatly boosted the high-quality information dissemination and expanded applications of photochromic soft materials.

Ionic Liquids as an Efficient Reaction Medium in the Robust Synthesis of ZnO Nanoparticles

Aim:: Ionic liquids belong to the class of green solvents and are distinguished by their simple yet distinctive physical properties that are related to their structure. These properties include their remarkable thermal stability, exceptional thermal conductivity, and negligible vapor pressure. Additionally, they are suitable and inert for a wide range of catalytic applications. Zinc Oxide Nanoparticles (ZnO-NPs) have been considered a cost-effective choice that requires modest reaction conditions to provide a high yield of the required products with remarkable selectivity in a short amount of time. Consequently, an investigation into the synthesis of ZnO-NPs in an ionic liquid medium has been attempted in the current work. Background:: The synthesis of metal nanoparticles using highly tunable ionic liquids is being investigated for many pharmacological applications and their usage in catalysis. Objectives:: In this context, the current work has used the co-precipitation approach to synthesize ZnO-NPs. The production of ZnO nanoparticles with a range of morphologies utilizing an imidazolium ionic liquid system has been the main topic of discussion. Methods:: The co-precipitation method has successfully been administered for the synthesis of morphologically diverse nano-crystalline ZnO particles using different ionic liquids, such as 1-propyl- 3-methylimidazolium bromide (pmim)(Br), 1-butyl-3-methylimidazolium bromide ([bmim][Br]), and 1-hexyl-3-methylimidazolium bromide (hmim)(Br) as an additive Results:: Modern analytical tools, including X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and FT-IR absorption spectroscopy have been employed to confirm the structure of these ZnO nanoparticles. The IR absorption peak below 480 cm-1 and the XRD pattern showed all the peaks in the diffraction diagram, revealing the formation of ZnO-NPs. FE-SEM images showed various morphologies of ZnO-NPs and they have been found to be separated from the agglomerated clusters. Conclusion:: The characteristic results have revealed ionic liquids to have substantial effects on the size of the zinc nano-species as well as provide the appropriate environment for the growth of the nanoparticles.

Ultrasound-Assisted Synthesis and DFT Studies of Novel Schiff Bases Derived from 3-Methyl-1,3-benzothiazol-2(3H)-one in an Ionic Liquid Medium

Ultrasound-Assisted Synthesis and DFT Studies of Novel Schiff Bases Derived from 3-Methyl-1,3-benzothiazol-2(3H)-one in an Ionic Liquid Medium

An Exceptional Valorization of CuO Nanoparticles in Ionic Liquids as an Efficient Medium for the Electrophilic Substitution of Indole Towards the Formation of Bis(indolyl)methanes

Aim: Ionic liquids are promising green solvents with simple but unique structure-related physical properties such as negligible vapour pressure, exceptional thermal conductivity, remarkable thermal stability and their suitability and inertness towards a broad range of catalytic applications. CuO NPs have been addressed as a cost-effective and a reagent of a choice that necessitates only mild reaction conditions to offer a high yield of the desired products with exceptional selectivity in a short duration of time. Therefore, in the present work, attempts have been made to explore the catalytic potentials of CuO NPs in an ionic liquid medium to synthesize biologically important bis(indolyl)methanes. Background: Catalytic explorations of metal oxide nanoparticles in ionic liquids offers a cooperative effect that has a significant impact on the kinetics as well as on the outcome of the reaction. Therefore, such catalytic systems in the present times have seized the scientific community's interest from the perspectives of sustainable development in synthetic organic chemistry. The combination of metal oxide nanoparticles with highly tunable ionic liquids is not only used to synthesize simple organic molecules but also explored in the synthesis of complex organic molecules of high commercial and biological relevance. Objectives: The current work offers a rapid and robust protocol for synthesizing bis(indolyl)methanes via electrophilic substitution reaction between indole and various aldehydes in the presence of a CuO nanoparticles-ionic liquid system. The discussion focuses on the high tolerance of different functionalities by the catalytic system leading to the synthesis of bis(indolyl)methanes. Methods: CuO NPs have been synthesized via the co-precipitation method using ionic liquid. The applicability of metal oxide nanoparticles-IL matrix was further investigated in synthesizing bis(indolyl)methanes. Results: The FT-IR absorption below 600 cm-1 and the XRD pattern showing all the peaks in the diffraction diagram revealed the formation of CuO NPs. FESEM images show the flake-shaped morphology of CuO NPs and are found to be separated from the agglomerated clusters Conclusion: Ionic liquid-CuO NPs matrix reveals good to exceptional catalytic properties, and their advancements as a catalytic system at room temperature open new avenues for synthetic organic chemists.

Microwave-enhanced hydrolysis of cellulose by acidic ionic liquids

In the [Bmim]Cl reaction medium, five different acidic ionic liquids were used as catalysts to study the effects of reaction time, reaction temperature, system water content, catalyst dosage, microwave power, and other factors on cellulose hydrolysis under microwave irradiation. The results showed that in the [Bmim]Cl reaction system, using N-methylpyrrolidone methylsulfonic acid salt as a catalyst, controlling the microwave reaction time at 10 min, reaction temperature at 130 °C, catalyst dosage at 1 g/g (cellulose), water addition at 0.756 μL/g ([Bmim]Cl), and microwave power at 480 W, resulted in the best cellulose hydrolysis effect with a glucose yield of 74.49%. Compared to conventional heating, the glucose yield increased by 24% and the hydrolysis time was reduced by 77%. Microwave irradiation significantly enhances the cellulose hydrolysis process in an ionic liquid medium.

Efficient in situ saccharification of microcrystalline cellulose over immobilized cellulase on magnetic biochar in ionic liquid media

Saccharification serves as the entry point for the biomass into biorefinery schemes and plays a vital role in lignocellulose transformation towards bio-fuels and platform molecules. Herein, an efficient in situ saccharification of lignocellulose under the mediation of ionic liquid of [DMIM]DMP is reported, using a series of magnetically-separable biochars as catalyst supports with immobilized endoglucanase Cel5A. The physicochemical properties of these magnetic biochars with immobilized endoglucanase (abbreviated as MBIE) were thoroughly characterized by FTIR, TG, SEM/EDX, XRD, XPS, N2 physisorption, UV–vis and VSM. The results revealed that the endoglucanase, which functions as the catalytically active species, was immobilized on the biochar via simultaneous physical adsorption and covalent attachment. The extremely high surface area of biochar endows a high loading of endoglucanase and easy diffusion of reactant within the catalyst’s framework. The zeta potential of the catalyst was − 7.06 mV, indicating its excellent stability. MBIE with immobilizing endoglucanase of 484.36 mg/g exhibited the superior performance under a biphasic system (IL/water v/v 5:1), affording a glucose yield of 932.5 mg/g. The activity of MBIE remained constant after 10 consecutive cycles via magnetic recycling. This work demonstrates an efficient in situ saccharification process catalyzed by the developed MBIE with high activity and excellent regeneration ability.

Another Piece of the Ionic Liquid's Puzzle: Adsorption of Cl- Ions.

Classical electrochemical and microscopy methods were used to characterize the interfacial processes of the adsorption of chloride ions from ionic liquids at the Bi(111) single crystal electrode. The mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium chloride was electrochemically characterized by using cyclic voltammetry and electrochemical impedance spectroscopy. In situ scanning tunneling microscopy images showed the formation of superstructures at the electrode's surface over an extended period of time. The specific adsorption of chloride ions reaches an equilibrium state in a more viscous ionic liquid medium slower than in aqueous and organic solvents. Capacitance values increase considerably (also depending on alternative current frequency) at the potential region, where the specific adsorption of chloride ions with partial charge transfer occurs.

Experimental and Theoretical Insight into the Ionic Liquid-Mediated Complexation of Trivalent Lanthanides with β-Diketone and Its Fluorinated Analogue.

A multitechnique approach with theoretical insights has been employed to understand the complexation of trivalent lanthanides with two β-diketones, viz. 1-phenyl-1,3-butanedione (L1) and 4,4,4-trifluoro-1-phenyl-1,3-butanedione (L2), in an ionic liquid (C6mim·NTf2). UV-vis spectral analysis of complexation using Nd3+ revealed the predominance of ML2+ and ML4- species. The stability constants for the PB complexes were higher (β2 ∼ 10.45 ± 0.05, β4 ∼ 15.51 ± 0.05) than those for the TPB (β2 ∼ 7.56 ± 0.05, β4 ∼ 13.19 ± 0.06). The photoluminescence titration using Eu3+ corroborated the same observations with slightly higher stability constants, probably due to the higher ionic potential of Eu3+. The more asymmetric (AL2ML4 ∼ 5.2) Eu-L2 complex was found to contain one water molecule in the primary coordination sphere of Eu3+ with more covalency of the Eu3+-O bond (Ω2L1 = 8.5 × 10-20, Ω4L1 = 1.3 × 10-20) compared to the less asymmetric Eu-L1 complex (AL1ML4 ∼ 3.5) with two water molecules having less Eu-O covalency (Judd-Offelt parameters: Ω2L1 = 7.3 × 10-20, Ω4L1 = 1.0 × 10-20). Liquid-liquid extraction studies involving Nd3+ and Eu3+ revealed the formation of the ML4- complex following an 'anion exchange' mechanism. The shift of the enol peak from 1176 to 1138 cm-1 on the complexation of the β-diketones with Eu3+ was confirmed from the FTIR spectra. 1H NMR titration of the β-diketones with La(NTf2)3 evidenced the participation of α-H of the β-diketones and protons at C2, C4, and C5 positions of the methylimidazolium ring. For the ML2 complex, 4 donor O atoms are suggested to coordinate to the trivalent lanthanides with bond distances of 2.3297-2.411 Å for La-O, 2.206-2.236 Å for Eu-O, and 2.217-2.268 Å for Nd-O, respectively, while for the ML4 complex, 8 donor O atoms were coordinated with bond lengths of 2.506-2.559 Å for La-O, 2.367-2.447 Å for Eu-O, and 2.408-2.476 Å for Nd-O. The Nd3+ ion was higher by 9.7 kcal·mol-1 than that of the La3+ ion for the 1:4 complex. The complexation energy with L1 was quite higher than that with L2 for both 1:2 and 1:4 complexes. Using cyclic voltammetry, the redox behavior of trivalent lanthanides Eu and Gd with β-diketonate in ionic liquid medium was probed and their redox energetic and kinetic parameters were determined.

Extraction of Palladium from Spent Nuclear Fuel Reprocessing Solutions

New solvent systems for selective separation of palladium from nuclear wastes represent a prospective way to reduce the total waste volume and induce this metal’s extraction. For this purpose, the potential of modern green solvent room-temperature ionic liquid was assessed with diamide-type extractants based on N-heterocycles and S-donating thiodiglicolic acid. The N-donating heterocyclic extractants demonstrate structure-dependent high selectivity toward palladium in the presence of various impurity metals (such as Zr, Cs, Sr, Mo, Ce, Fe, and Cr) from spent nuclear fuel. Palladium is extracted into the organic phase quite selectively with a separation factor greater than a thousand for all extractants. Ionic liquid media are capable of selective palladium separation from platinum group metals and synergetically increase the selectivity of the extractants.

Elucidating the Iron‐Based Ionic Liquid [C4py][FeCl4]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

AbstractIn this study, a low‐melting organic‐inorganic crystalline ionic liquid compound, N‐butyl pyridinium tetrachlorido ferrate (III) is described. The material can easily be synthesized using a one‐pot approach in an ionic liquid medium. Single‐crystal X‐ray diffraction confirms that the basic inorganic block is [FeCl4]−, which is counterbalanced by an N‐butyl pyridinium cation. The compound exhibits a melting point of 37.6 °C by differential scanning calorimetry, which is among the lowest values for a pyridinium‐based metal‐containing ionic liquid. The material shows promising electrochemical behavior at room temperature in both aqueous and nonaqueous solvents, and at elevated temperatures in its pure liquid state. Given its appreciable solubility in both water and acetonitrile, the compound can act as a redox‐active species in a supporting electrolyte for redox flow battery applications. These classes of low‐melting ionic solids with long‐range order and interesting electrochemical applications are potential candidates for a range of green energy storage and harvesting systems.

Electrochemical oxidation of dicarbonylcyclopentadienylcobalt(I) in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ionic liquid

The electrochemical oxidation of the 18-electron half-sandwich organometallic complex [Co(η5-C5H5)(CO)2], 1, has been studied in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [bmpyr][NTf2], and in dichloromethane, CH2Cl2, containing [bmpyr][NTf2] as the supporting electrolyte. In the ionic liquid, the 17-electron cation 1+ is generated under voltammetric conditions via a process that has a reversible mid-point potential (Em) of 0.22 V vs. Fc0/+ (Em = 0.23 V vs. Fc0/+ in CH2Cl2/[bmpyr][NTf2]). 1+ reacts with 1 to form the cationic dimer [Co2(η5-C5H5)2(CO)4]+, 2+, which reacts with [NTf2]− to form cobaltocenium, Cc+, and [Co(NTf2)n](n−2)− (with n = 2, 4, or 6) complexes as the products of bulk electrolysis. A second voltammetric oxidation process at more positive potential is associated with the oxidation of 2+ (Em = 0.62 V vs. Fc0/+ in [bmpyr][NTf2] and 0.72 V vs. Fc0/+ in CH2Cl2/[bmpyr][NTf2]) to form 22+, which accelerates the formation of Cc+ and [Co(NTf2)n](n−2)− complexes, which are reduced to cobaltocene and cobalt metal under conditions of cyclic voltammetry and bulk electrolysis. Mechanistic details and the reaction products have been characterised by cyclic voltammetry, chronocoulometry, bulk electrolysis, and FT-IR, UV–Vis and ESR spectroelectrochemical measurements. This investigation reveals how ionic liquid media may influence the electrochemical oxidation mechanism of half-sandwich metal and other complexes.

Comparing π-complexation capabilities of ionic liquids containing silver(I) and copper(I) ions by headspace single drop microextraction in combination with high-performance liquid chromatography.

Selective π-complexation capabilities of silver(I) and copper(I) ions can be effectively facilitated in ionic liquids. To understand the effects of environmental factors that influence the π-complexation of these metal ions with analytes, techniques that employ small volumes of ionic liquid that can be readily analyzed are desired. In this study, headspace single drop microextraction coupled with HPLCis used to investigate a diverse set of environmental factors on the metal ion-mediated complexation with aromatic compounds in ionic liquid media. Silver(I) and copper(I) bis[(trifluoromethyl)sulfonyl]imide salts were both studied by dissolving them in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ionic liquid and employing the mixture as extraction media for aromatic compounds. Water and acetonitrile within the sample solution were observed to interfere with the complexation of silver(I) ions and aromatic compounds, while ethylene glycol and triethylene glycol did not. The temperature and extraction times were optimized to fully facilitate the π-complexation capabilities of metal ions in ionic liquid media. Partition coefficients between the sample headspace and metal ion were determined using a three-phase equilibria model. Although no discernable difference in analyte partitioning between the headspace and ionic liquid solvent was observed, analyte partition coefficients to silver(I) ion tended to be greater compared to copper(I) ion.

Preparation of Thermoplastic Cellulose Esters in [mTBNH][OAC] Ionic Liquid by Transesterification Reaction.

The transesterification of cellulose with vinyl esters in ionic liquid media is suggested as a prospective environmentally friendly alternative to conventional esterification. In this study, various long-chain cellulose esters (laurate, myristate, palmitate, and stearate) with a degree of substitution (DS) up to 1.8 have been synthesized in novel distillable ionic liquid, [mTBNH][OAC]. This IL has high dissolving power towards cellulose, which can improve homogeneous transesterification. Additionally, [mTBNH][OAC] has durability towards recycling and can be regenerated and re-used again for the next cycles of esterification. DMSO is used as a co-solvent because of its ability to speed up mass transport due to lower solvent viscosity. The optimization of the reaction parameters, such as co-solvent content, temperature (20-80 °C), reaction time (1-5 h), and a molar ratio of reactants (1-5 eq. AGU) is reported. It was found that within studied reaction conditions, DS increases with increasing reaction time, temperature, and added vinyl esters. Structure analysis using FTIR, 1H, and 13C NMR after acylation revealed the introduction of the alkyl chains into cellulose for all studied samples. The results also suggested that the substitution order of the OH group is C7-O6 > C7-O2 > C7-O3. Unique, complex thermal and rheological investigation of the cellulose esters shows the growth of an amorphous phase upon the degree of substitution. At the same time, the homogeneous substitution of cellulose with acyl chains increases the melt viscosity of a material. Internal plasticization in cellulose esters was found to be the mechanism for the melt processing of the material. Long-chain cellulose esters show the potential to replace commonly used externally plasticized cellulose derivatives.

Nanocomposite Polymer Gel Electrolyte Based on TiO2 Nanoparticles for Lithium Batteries.

In this article, the specific features of competitive ionic and molecular transport in nanocomposite systems based on network membranes synthesized by radical polymerization of polyethylene glycol diacrylate in the presence of LiBF4, 1-ethyl-3-methylimidazolium tetrafluoroborate, ethylene carbonate (EC), and TiO2 nanopowder (d~21 nm) were studied for 1H, 7Li, 11B, 13C, and 19F nuclei using NMR. The membranes obtained were studied through electrochemical impedance, IR-Fourier spectroscopy, DSC, and TGA. The ionic conductivity of the membranes was up to 4.8 m Scm-1 at room temperature. The operating temperature range was from -40 to 100 °C. Two types of molecular and ionic transport (fast and slow) have been detected by pulsed field gradient NMR. From quantum chemical modeling, it follows that the difficulty of lithium transport is due to the strong chemisorption of BF4- anions with counterions on the surface of TiO2 nanoparticles. The theoretical conclusion about the need to increase the proportion of EC in order to reduce the influence of this effect was confirmed by an experimental study of a system with 4 moles of EC. It has been shown that this approach leads to an increase in lithium conductivity in an ionic liquid medium, which is important for the development of thermostable nanocomposite electrolytes for Li//LiFePO4 batteries with a base of lithium salts and aprotonic imidasolium ionic liquid.

Numerical simulation and new controller design of steerable nano-mirror in ionic liquid electrolytes

This research aims to create a novel controller for micro/nano-systems (sensors and actuators) operating in ionic liquid media. To illustrate the capability of the proposed controller based on numerical simulation, the controller’s impacts on a nano-mirror immersed in ionic liquid media are analyzed. Based on the modified couple stress theory, a two-degree-of-freedom descriptive formulation is developed to more precisely investigate the size-dependent dynamic performance of nano-mirrors. Also, nano-mirror physics is extended by employing resistive fluid as a continuum substance ranging from light to dense. Utilizing the lattice Boltzmann method, the dynamic performance of the nano-mirror is studied. Considering numerical results, a new model-based self-adaptive controller is designed and added to the system. Furthermore, a classical controller is designed. Finally, the advantages of the proposed methodology are compared with the results of classical control methods employed in such systems, for which a numerical model of the system’s dynamic behavior is developed.

Efficiently adsorption and degradation of Blue 133 and Reactive Red 66 dyes under UV and visible light using Tin(II) oxide/chitosan in ethyl pyridinium iodide ionic liquid

ABSTRACT The expansion of dye pollutants overburdened the environment and consequently increased pollution. Photodegradation and adsorption are one of the most efficient processes for water treatment. Metal oxides have been studied for this application. Amongst of metal oxides, Tin(II) oxide semiconductor and its modification are interesting. In this work, Tin(II) oxide nanoplates/chitosan in an ionic liquid media was prepared. This mild method was done in ethyl pyridinium iodide ionic liquid. The structural character of this composite was examined by XRD, TEM, AFM, and DRS techniques. The TEM results showed that this composite consisted of plate morphology. The photocatalysis experiments were carried out by irradiating in ultraviolet and visible light of dyes containing Blue 133 (B133), and Reactive Red 66 (R66). By combining the good semiconductor properties of Tin(II) oxide and the high adsorption of chitosan, the composite is promising for the photocatalytic removal of organic dyes. The Langmuir adsorption isotherm model was used to study the adsorption-photodegradation process of dye molecules on this composite. The results revealed that the highest removal efficiency of Blue 133 under visible light was 45.48%, whereas achieved under ultraviolet light 98.41%. Also, the degradation percentage of Reactive Red 66 by composite remained 98.85%, under ultraviolet light, the removal efficiency decreased to 46.12%, while visible light. The presence of chitosan enhanced the photodegradation-adsorption properties directed towards visible light.