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Background: The non-covalent molecular interactions of 1-Ethyl-3- methylimidazolium chloride-aluminum chloride and pure alcohols are attracting attention in the industry, academic and research. Chemists, engineers, designers, and some researchers are interested in accessing trustworthy databases. Objective: 1-Ethyl-3-methylimidazolium chloride-aluminum chloride interacts with pure alcohols with non-covalent interactions. Physicochemical properties with their convincing data interpret the interactions occurring there. Mehtods: For that limiting apparent molar volume, molar refraction, and limiting apparent molar isentropic compressibility of the binary systems viz., ([EMIm]Cl/AlCl3) +methanol, ([EMIm]Cl/AlCl3) +ethanol, ([EMIm]Cl/AlCl3) +1-propanol, and ([EMIm]Cl/AlCl3)+ 1-butanol have been calculated using physicochemical properties i.e.,. density, refractive index, and speed of sound, respectively within the temperature range T=293.15K-318.15K (with the interval of 5K). Results: The ionic liquid strongly interacts with 1-butanol (106⋅φov =874.52 m3 mol-1, 106·RM = 211.13 m3 mol-1, and 10-11·φok= -0.10 m3 mol-1 Pa-1, 108· (∂φoE/∂T)P = 1.52 m3 mol-1 K-2) than other chosen primary alcohol at a higher temperature (318.15K). Among the individual ions, the 106·φov(ion) is higher for ALCI4-(522.96 m3 mol-1) than [EMIm]+ (351.56 m3 mol-1) at high temperature (318.15K) in 1-butanol. Conclusion: The molecular interactions occurring between the ionic liquid and solvent molecules are due to the structure-making capacity caused by intermolecular forces and non-covalent interactions. Where the 1-butanol strongly interacts with ionic liquids. In between the ions, the anaion interaction is greater than cation to solvents.

Urea/1-ethyl-3-methylimidazolium chloride (urea-EMIC) was developed to electrodeposit Cu from Cu2O at room temperature. Density, viscosity and conductivity of this urea-EMIC system were obtained. The cyclic voltammograms illustrated that the electroreduction of copper ion (Cu(I) ion) involves a quasi-reversible and one-step single electron transfer process. Chronoamperometric studies showed that the copper electrodeposition proceeds a three-dimensional (3D) progressive model. With an increase in temperature, on voltammograms the onset potentials for copper ion reduction shifted anodically and the diffusion coefficient determined using chronoamperometry increased from 5.40 × 10−11 m2 s−1 at 333 K to 1.02 × 10−10 m2 s−1 at 363 K. Also, potentiostatic electrolysis was conducted on tungsten substrates at − 0.65 V (vs. Ag) and 363 K. Then spherical metallic copper electrodeposits were obtained.

The recycling of SO2 is very meaningful not only to the environmental protection but also to the sulfur resource utilization. To realize the recycling of SO2, developing green solvents that enable effective, selective and reversible absorption of SO2 is demanded. In this work, we innovatively found that 1-ethyl-3-methylimidazolium chloride ([emim]Cl) and dicyandiamide (DCDA) can form a new kind of deep eutectic solvents (DESs). The physiochemical properties of [emim]Cl+DCDA DESs were characterized to provide the fundamental data of DESs first. Subsequently, the SO2 absorption performance of [emim]Cl+DCDA DESs were systematically investigated. It is found that the absorption of SO2 in [emim]Cl+DCDA DESs is fast, and the capacities of SO2 absorption are very high (16.58 mol/kg at 298.2 K and 104.7 kPa, and 2.45 mol/kg at 298.2 K and 1.7 kPa). In addition, the absorption of SO2 in [emim]Cl+DCDA DESs is highly selective towards CO2 and N2, and also highly reversible in consecutive absorption-desorption cycles. Finally, the underlying mechanism for SO2 absorption in [emim]Cl+DCDA DESs was examined by quantum chemistry calculations and spectroscopic characterizations.

An eco-friendly and economically viable electrochemical exfoliation method has the potential to produce few-layer graphene as a support for a dendritic Pt nanoparticle modified electrode for better non-enzymatic electrooxidation of glucose.

In this work, the conductivity (k) of Lewis acidic ionic liquid (IL) comprising a melt of organic chloride and aluminum chloride (AlCl3) with different molar ratios of organic chlorides with AlCl3 in the temperature range of 70-110 °C are reported. The ILs prepared with three imidazolium-based organic chlorides such as EMIC, BMIC, and HMIC are studied. The molar ratios of 1:1.5, 1:1.8, and 1:2.0 are selected for the study to maintain the acidity of the ILs for possible metal electrodeposition applications. The electrochemical behavior of anion species in the three ILs is studied using electrochemical impedance spectroscopy (EIS) technique and obtained the precise and fast measurement of conductivity values. The measured k values of all the ILs followed the Arrhenius law. The activation energies of conduction determined by fitting the experimental conductivity data are in good agreement with the literature. The conductivity of ILs with lower alkyl group organic chlorides decreased with the higher mole fraction of AlCl3. In contrast, the conductivity of IL having a higher alkyl group organic chloride (HMIC) increased with the increasing mole fraction of AlCl3. Based on the thermodynamic calculations, the differences in conductivities are attributed to the anion concentration, the molecular structure, cation-anion interactions, and hydrogen bonds in the ILs.

Electrochemical double-layer capacitors (EDLCs) have recently received an enormous attraction due to their ability to produce higher power density without compromising the durability. Producing cheaper, safer, and more durable devices obviously brings more benefits to the modern world applications. This investigation was carried out to optimize an ionic liquid (IL)–based gel polymer electrolyte (GPE), to fabricate an EDLC using the optimized electrolyte with natural graphite electrodes, and to characterize the performance of the device. Electrolyte was prepared with the IL, 1-ethyl-3-methylimidazolium chloride (1E3MICl); the polymer poly(vinylidenefluoride)-co-hexafluoropropylene (PVdF-co-HFP); and the salt, zinc chloride (ZnCl2). The electrochemical properties of the electrolyte were evaluated by electrochemical impedance spectroscopy (EIS), DC polarization test, and linear sweep voltammetry (LSV), and the EDLC was characterized by EIS, cyclic voltammetry (CV), and galvanostatic charge–discharge (GCD) test. The optimum composition was found to be 26% PVdF-co-HFP:52% ZnCl2:22% 1E3MICl (weight percentages) with the room temperature conductivity of 1.85 × 10−3 S cm−1 and ionic transference number of 0.72. EDLC exhibited a single-electrode specific capacitance of 4.92 F g−1 with 65% retention over 1000 cycles as per CV test. In the GCD results, the EDLC was able to held discharge capacitance of 3 F g−1 for complete 1000 cycles. The durability of the EDLC with this IL-based GPE shows a great potential in the energy applications with further enhancements.

The capture of SO2 from industrial tail gas is of great significance to control air pollution and reserve sulfur resource. In this work, we proposed the use of deep eutectic solvents (DESs) formed ...

Superacid VNU-11–SO4, a modified metal–organic framework by post-synthetic treatment with a sulfuric acid solution, has been considered as a promising heterogeneous catalyst in the isomerization of glucose to fructose and further dehydration to form 5-hydroxymethylfurfural (HMF) due to its possession of both Lewis and Bronsted acid sites. In this work, we focused on using VNU-11–SO4 for the optimization of the conversion of fructose and glucose into HMF using an ionic liquid as a green solvent. The highest yields of HMF from glucose and fructose could be obtained in 28% (140 °C, 8 h) and 86% (110 °C, 3 h), respectively, with the use of VNU-11–SO4 catalyst in 1-ethyl-3-methylimidazolium chloride ionic liquid. Recycling examination of the catalyst showed only a slight decrease in the HMF yield, implying its potential industrial application in biomass transformation.

The removal of SO2 from flue gas for the improvement of atmospheric quality and human health has attracted sustainable attention. In this work, 1-ethyl-3-methylimidazolium chloride (EmimCl) was pai...

The effects of three pyridine derivative additives, 4-hydroxypyridine, 4-picolinic acid, and 4-cyanopyridine, on Al-Mn coatings were investigated in 1-ethyl-3-methylimidazolium chloride-AlCl3-MnCl2 (EMIC-AlCl3-MnCl2) ionic liquids. The smooth mirror-like bright Al-Mn coatings were obtained only in the EMIC-AlCl3-MnCl2 ionic liquids containing 4-cyanopyridine, while the matte Al-Mn coatings were electrodeposited from EMIC-AlCl3-MnCl2 without additives or containing either 4-hydroxypyridine or 4-picolinic acid. The scanning electron microscope and X-ray diffraction showed that the bright Al-Mn coatings consisted of nanocrystals and had a strong (200) preferential orientation, while the particle size of matte Al-Mn coatings were within the micron range. The brightening mechanism of 4-cyanopyridine is due to it being adsorbed onto the cathode to produce the combined effect of (1) generating an overpotential to promote Al-Mn nucleation, (2) inhibiting the growth of the deposited nuclei and enabling them grow preferentially, making the coating composed of nanocrystals and with a smooth surface. The brightening effect of 4-cyanopyridine on the Al-Mn coatings was far better than that of the 4-hydroxypyridine and the 4-picolinic acid. In addition, the bright Al-Mn coating was prepared in a bath with 6 mmol·L−1 4-cyanopyridine and displayed superior corrosion resistance relative to the matte coatings, which could be attributed to its unique nanocrystalline structure that increased the number of grain boundaries and accelerated the formation of the protective layer of the corrosion products.

Two polysaccharides (cellulose and chitosan) and polyurethane dissolved in 1-ethyl-3-methylimidazolium chloride represented the matrix for the obtainment of new composite formulations comprised of lignin, ferrite–lignin hybrid and ketoconazole. The mechanical performances (Young’s modulus and compressive strength) increased with the filler addition. The nature of the filler used in the studied formulations influenced both bioadhesion and mucoadhesion parameters. It was found that the incorporation of lignin and ferrite–lignin hybrid into the matrix has influenced the in vitro rate of ketoconazole release, which is described by the Korsmeyer–Peppas model. All materials exhibited activity against Gram positive (Staphylococcus aureus ATCC 25923) and Gram negative (Escherichia coli ATCC 25922) bacteria.

Equilibrium data were obtained for aqueous two-phase systems composed of ionic liquid (IL) and two inorganic salts (dibasic potassium phosphate, K2HPO4, and tripotassium phosphate, K3PO4) at 298.15 K. The evaluated ionic liquids were 1-butyl-3-methylimidazolium methanesulfonate ([C4mim][CH3SO3]), 1-butyl-3-methylimidazolium chloride ([C4mim][Cl]), and 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]). Equilibrium curves of salt and ionic liquid were determined. Additionally, each curve was fitted into three mathematical models. The aqueous two-phase system composed of the IL [C2mim][Cl] required a lower mass fraction of IL and salt to form the systems than the other two systems studied in this work containing [C4mim][Cl] and [C4mim][CH3SO3]. Furthermore, the type of inorganic salts studied did not affect the equilibrium curves for the same ionic liquid.

We report that deep eutectic solvents can be formed by biobased aprotic organic compound succinonitrile (SN) functionalized as the hydrogen bond donor with solid ionic liquid 1-ethyl-3-methylimidaz...

A LiBr-[EMIM]Cl/H2O ternary system has been suggested as an alternative absorption working pair in this work. The crystallization temperature, vapor pressure, specific heat capacity, specific enthalpy, specific entropy, density, and viscosity of this ternary system at a mass ratio of 2.5:1 (LiBr/[EMIM]Cl) were measured systematically. The results showed that the vapor pressure of the LiBr-[EMIM]Cl/H2O was nearly identical to that of LiBr/H2O at an 8.5% lower mass fraction. Under the same absorption ability, LiBr-[EMIM]Cl/H2O had a crystallization temperature much lower than LiBr/H2O, as well as much lower viscosity than ionic liquids. LiBr-[EMIM]Cl/H2O shows a certain potential as an alternative working pair in the absorption heat pump system.

Впервые были измерены токи обмена на границе алюминия с хлоралюминатной ионной жидкостью (ИЖ) 1-этил-3-метилимидазолий хлорид методом фадеевского импеданса. Ток обмена на границе алюминия с кислой ИЖ, в которой присутствует анион Al2Cl7–, на 3 порядка выше тока обмена на границе алюминия с нейтральной ИЖ. Следовательно, ион Al2Cl7– является основной электроактивной частицей в расплаве. В кислых ИЖ ток обмена не зависит от мольной доли хлорида алюминия в ИЖ и составляет 1.6 мА∙см-2. The exchange currents at the interface between aluminum and chloroaluminate ionic liquid (IL) 1-ethyl-3-methylimidazolium chloride were measured for the first time by impedance spectroscopy. The exchange current values at the interface between aluminum and acidic IL is three orders of magnitude higher than at the interface between aluminum and neutral IL because of Al2Cl7– anion existence. Therefore, the Al2Cl7– ion is the main electroactive particle in the melt. The exchange current in acidic ILs does not depend on the molar fraction of aluminum chloride in IL and is equal to 1.6 mA∙cm-2.

The density, sound velocity, and viscosity of 1-ethyl-3-methylimidazolium chloride [C2mim]Cl in pure water and aqueous solutions of some electrolytes such as potassium chloride, potassium carbonate, as well as potassium phosphate (weight fraction of salt fixed at ws = 0.11) have been measured over a wide range of temperatures from 298.15 to 318.15 K. The obtained experimental data has been used to compute various volumetric, compressibility, and viscometric parameters, e.g. apparent molar properties, limiting apparent molar and transfer properties. The co-sphere overlap model was employed to describe the dominant intermolecular interactions in the ternary solutions. Additionally, the structure making/breaking nature of the [C2mim]Cl in the ternary solutions has been discussed in terms of Hepler’s constant and the temperature derivative of viscosity B-coefficient (dB⁄dT). The activation free energy of solvent and solute, activation enthalpy, and activation entropy have been calculated by the application of transition state theory. The calculated parameters have been interpreted in the sense of solvent-solute and solute-solute interactions. The Fourier transform infrared (FTIR) studies also have been done for the studied systems. Volumetric, acoustic, viscometric, and spectroscopic studies can render some evidence and help to understand the aqueous solution behavior of ionic liquids.

Mjerene su gustoće umjereno razrijeđenih otopina 1-etil-3-metilimidazolijevog klorida (EMImCl) u butan-2-olu pri različitim temperaturama,  = 15, 20, 25 i 30 °C. Iz dobivenih gustoća, određena su volumetrijska svojstva (prividni i parcijalni molarni volumeni) EMImCl u butan-2-olu. Korištenjem Massonove jednadžbe izračunati su prividni granični molarni volumen i interakcijski koeficijent. Iz prividnog graničnog molarnog volumena, određenog pri različitim temperaturama, također je izračunata prividna granična molarna ekspanzibilnost za EMImCl u butan-2-olu pri svim radnim temperaturama – ti su podaci dali uvid u svojstva EMImCl u butan-2-olu. The densities of moderately dilute solutions of the 1-ethyl-3-methylimidazolium chloride (EMImCl) in butan-2-ol were measured (using Anton-Paar DMA 4500M densimeter) at diferent temperatures,  = 15, 20, 25 and 30 °C. From the obtained density data, volumetric properties (apparent molar volumes and partial molar volumes) have been evaluated. The volumetric data have been analyzed using Masson's equation. The limiting apparent molar volume or partial molar volume at infinite dilution, and the slope of Masson's equation at different temperatures for EMImCl in butan-2-ol have been interpreted in terms of ionion and ion-solvent interactions, respectively. In addition, negative values in the whole temperature range for the limiting apparent molar expansibility indicates structure breaking properties of EMImCl in butan-2-ol.

Cellulose nanocrystals were prepared using ionic liquids (ILs), 1-ethyl-3-methylimidazolium chloride [EMIM][Cl] and 1-propyl-3-methylimidazolium chloride [PMIM][Cl], from microcrystalline cellulose. The resultant samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The XRD results showed that nanocellulose obtained by treatment with both ILs preserved basic cellulose I structure, but crystallinity index of samples (except for Sigmacell treated with [EMIM][Cl]) was lower in comparison to the starting microcrystalline cellulose. The DLS results indicated noticeably smaller particle sizes of prepared cellulose for material treated with [PMIM][Cl] compared to cellulose samples hydrolyzed with [EMIM][Cl], which were prone to agglomeration. The obtained nanocellulose had a rod-like structure that was confirmed by electron microscopy analyses. Moreover, the results described in this paper indicate that cation type of ILs influences particle size and morphology of cellulose after treatment with ionic liquids.

Aluminum (Al) coatings, which are found to be dendrites, have been deposited on uranium (U) substrate in ionic liquid via galvanic displacement. Interestingly, a dense Al nano-layer has formed between the Al dendrites and the U substrate. In this work, the growth mechanism of the Al coating has been investigated by ultraviolet–visible spectroscopy, scanning electron microscopy, grazing incidence X-ray diffraction, and electrochemical measurements: the galvanic reaction sees the oxidation of U from the substrate while Al2Cl7− are reduced on its surface, driven by the electrochemical potential difference between Al and U. Furthermore, we have found that the Al nano-layer passivates the uranium surface, which is proved to be the rate limiting step in the galvanic deposition process; the observation of the interface morphology evolution process indicates that this Al nano-layer grows in a three-dimensional mode. This work demonstrates a convenient approach to deposit dense Al nano-layer on U, without any external power source.

In this paper, a silicalite-1 modified HY zeolite (HY/silicalite-1) was prepared and applied as an efficient catalyst to promote the hydrolysis of microcrystalline cellulose to glucose in ionic liquid 1-ethyl-3-methylimidazolium chloride ([Emim]Cl). Scanning Electron Microscope reflects a core–shell morphology of HY/silicalite-1. When using HY/silicalite-1 as catalyst instead of non-modified HY, the glucose selectivity could be significantly improved, and the hydrolysis temperature could also be reduced to 110 °C. Under optimal conditions, 93.5% of total reducing sugar and 50.8% of glucose yield were obtained within 8 h of the reaction. The mechanism with respect to the hydrolysis of cellulose over HY/silicalite-1 was fully discussed. The improved sugar selectivity may due to reduced Lewis acidity of modified HY. Moreover, the reduced contact probability of sugar with the Lewis acid cites of catalyst caused by the outer silicalite-1 layer may also contribute to the good sugar selectivity.

In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride ([emim]Cl) as the entrainer to separate tert-butyl alcohol (TBA) + water. We measured the isobaric vapor–liquid equilibrium (VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.

The selective removal of H2S from CO2-contained gaseous mixture is an important and challenging task for natural gas industry. Herein, 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) + imidazole DESs were examined as the physical solvents for H2S and CO2 absorption. The solubilities of gases were determined systematically, and the Henry’s constants of gases, ideal selectivities of gas pair, enthalpy changes of gas absorption were calculated. The variations of H2S and CO2 solubilities with [Emim]Cl contents in DESs show different trends. In addition, the H2S solubilities in the [Emim]Cl + imidazole DESs are much higher than those of CO2. The results were compared with other liquid solvents, and [Emim]Cl + imidazole DESs enable extremely high efficiency for H2S absorption and large selectivity towards CO2. The molecular dynamics (MD) simulations and density functional theory (DFT) calculations were then systematically carried out to explain the results obtained. It is demonstrated that the strong interaction was found between the H of H2S and Cl− of [Emim]Cl, which contributes to the excellent performance of [Emim]Cl + imidazole DESs in separation of H2S from CO2.

Al-ion batteries technology is receiving growing attention thanks to the high natural abundance of aluminum and to the high energy density that can be obtained with a three-electron redox process. In this work, the physicochemical properties of the room temperature ionic liquid composed of aluminum chloride and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) were systematically investigated by varying the molar ratio AlCl3/[EMIm]Cl in the range 1.11.7. The combined use of multinuclear (Al-27, C-13, H-1) NMR, electrochemical impedance spectroscopy, and thermal analysis allowed us to shed light on the structureproperties relationships of this complex system, also resolving some controversial conclusions of previous literature. We showed that the 1.2 molar ratio is the best compromise between high ionic conductivity and the use of the highly toxic AlCl3. This electrolyte was tested in a standard Al-ion cell and gave promising results even at very high current densities (i > 200 mA g(-1))

The mechanism of aluminium reduction in 1-ethyl-3-methylimidazolium chloride/chloroaluminate ionic liquids has been investigated. Stationary polarisation curves for aluminium electrode in 1-ethyl-3-methylimidazolium chloride chloroaluminate ionic liquid are S-shaped and contain limiting current plateau sections, which indicates heterogeneous kinetics of aluminium electrochemical reduction. The shift in the half-wave potential on the voltammograms may be interpreted using the model of the homogeneous chemical reaction preceding the electrochemical reduction of aluminium. Limiting current values have been obtained for the first time. The limiting currents grow with the increase in the concentration of Al2Cl7– anion and are determined by the diffusion of Al2Cl7– particle. The limiting current density in the neutral liquid (4.39 μA·cm−2) is by 3–4 orders of magnitude lower than the maximum current densities in acidic liquids (1.81 – 25.37 mA·cm−2 at 1.1 ≤ N ≤ 2.0). The possible preceding homogeneous chemical reaction has a much higher rate constant compared to the diffusion rate constant. Aluminium is reduced from Al2Cl7– anion at overvoltages below 1.5 V. At overvoltages above 1.5 V aluminium can be reduced from AlCl4– anion, and at the overvoltage of 2.2 V the reduction of [EMIm]+ becomes possible. The values for the diffusion coefficient of Al2Cl7– anion in the IL at different concentrations of Al2Cl7– have been determined to evaluate the contribution of migration flow to the total flow of ions at 30 °C. The diffusion coefficient of Al2Cl7– anions was found to be 9.3·10−7 cm2·s−1. It was shown that the thickness of the diffusion layer in the investigated electrochemical system decreases with the increase of Al2Cl7– concentration.

Electrodeposition of palladium in ionic liquids has not been actively investigated. Herein, the electrochemistry of PdCl2 for electrodeposition of palladium in 1-Ethyl-3-Methylimidazolium Chloride ([EMIM][Cl]) ionic liquid (IL) was studied at a Pt-Ir working electrode. A rotating disc was applied to allow a better understanding of the reaction kinetics. A range of techniques, such as cyclic voltammetry (CV) and current-time transient, were used to elucidate the electrochemistry of palladium of PdCl2 in [EMIM][Cl] IL under both stationary and rotating conditions. Two cathodic waves and two anodic waves were observed in CV. We propose that both of the cathodic peaks, which are separated by the surface alteration of the electrode during the cathodic scan, are produced by the electroreduction of PdCl42- to palladium, with their characteristics of mixed kinetics and mass transfer controlled, respectively. Regarding the nucleation of palladium on Pt-Ir electrode, a 3D, instantaneous nucleation mechanism was proved under quiescent conditions. The nucleation of Pd at rotating disc electrode(RDE) was fmodeled, and it was found that RDE promote instantaneous nucleation of Pd.

In this study, we dissolved PbO in a new electrolyte urea/1-ethyl-3-methylimidazolium chloride (EMIC) and electrochemically extracted Pb. The electrochemical behavior of lead was investigated using chronoamperometric and cyclic voltammetric techniques. The cyclic voltammograms illustrated that lead reduction is quasi-reversible and follows a single-step, two-electron transfer process. The chronoamperometric experiments showed that lead reduction in the PbO–urea/EMIC system follows a 3D instantaneous nucleation and a diffusion-controlled growth at 353 K. The diffusion coefficient was 1.67 × 10−8 cm2 s−1. The effect of temperature on the electrochemical behavior of lead was investigated. Results showed that electrode reaction becomes more reversible as temperature increases from 343 to 373 K. The diffusion coefficients increase with increasing temperature and obey the Arrhenius' law. The activation energy is estimated to be 38 kJ mol−1. Electrodeposition experiments were conducted on tungsten substrates at different negative potentials and various temperatures. Scanning electron microscopy (SEM) images of electrodeposits showed that the Pb particles became smaller and are more densely distributed at more negative potentials and higher temperatures. The obtained electrodeposits were metallic lead, as verified by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS).

This work studied the electrodeposition of aluminum (Al) coating on uranium (U) substrate from aluminum chloride (AlCl3)-1-ethyl-3-methylimidazolium chloride (EMIC) ionic liquid at room temperature. The coating was characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The adhesion between the coating and U substrate was estimated by thermal shock test. The corrosion resistance of the coating was evaluated by open circuit potential and potentiodynamic polarization testing in 3.5 wt.% NaCl solution. Results indicated that anodic etching of U in AlCl3-EMIC ionic liquid favored the adhesion of Al coating to U substrate by complete removal of the oxide on U surface. The inter-diffusion between Al and U at the interface was also observed. A uniform, compact and smooth coating was obtained at the current density of 20 mA/cm2. The Al coating significantly enhanced the corrosion resistance of U by reducing the corrosion current density by one order of magnitude.

V diplomskem delu smo prikazali vpliv različnih sestav elektrolita iz 1-etil-3-metilimidazolijevega klorida (EMIMCl) in aluminijevega klorida (AlCl3) na delovanje aluminij-organskega akumulatorja. In this thesis we have shown the influence of different compositions of 1-ethyl-3-methylimidazolium chloride (EMIMCl) and aluminium chloride (AlCl3) electrolytes on the performance of aluminium-organic secondary battery.

Aqueous systems composed of ionic liquid make up a new alternative for use in processes involving the separation of biomolecules. The objective of this experiment was to obtain the thermo-physical properties of density, refractive index, electrical conductivity, molar volume, thermal expansion coefficient and apparent specific volume of the ionic liquid 1-ethyl-3-methylimidazolium chloride. The thermo-physical properties of aqueous solutions of this ionic liquid were measured as a function of the mass fraction w = (0.05, 0.125, 0.2, 0.275 and 0.35), temperature T = (293.15, 303.15, 313.15 and 323.15) K and pH = (7.5, 8.0 and 8.5). Models representing the combined effects between variables were fit since they are required for industrial applications where the physical parameters must be accurately calculated. Models representing the combined effects of the variables temperature, mass fraction and pH values of ionic liquid were adjusted and presented good fit.

The anodic dissolution of copper was investigated at a copper RDE in the Lewis acidic and basic composition regions of the room-temperature AlCl3-EtMeImCl ionic liquid (IL) to assess the utility of chloroaluminate liquids as solvents for the electrochemical machining and electropolishing of copper. In the Lewis acidic IL (60 mol % AlCl3), the dissolution of Cu0 proceeds under mixed kinetic-mass transport control with an exchange current density of 7.00 mA cm−2 at 306 K and an apparent activation free energy of 19.7 kJ mol−1. A formal potential of 0.843 V was obtained for the Cu+/Cu0 reaction from potentiometric measurements. In the basic IL (< 50 mol % AlCl3), potentiometric measurements showed that the oxidation of Cu0 resulted in the formation of [CuCl2]−. In this case, the formal potential of the [CuCl2]−/Cu0 reaction is −0.412 V. At small positive overpotentials, the reaction exhibited mixed control and was first order in the chloride concentration, indicating that only a single Cl− is involved in the RDS. However, at more positive overpotentials, the reaction transitions to mass transport control, and a well-defined limiting current is observed for the anodization process. This limiting current scales linearly with the free chloride concentration in the IL.

Electrodeposition of palladium from ionic liquids has not been actively studied although this new class of electrolytes offer certain important advantages. Further, the application of rotating disc technique for kinetic studies in ionic liquids is scarce, and absent from the studies on Pd. In this work, the rotating disc electrode (RDE) technique was used to study the electrochemistry of PdCl2 dissolved in 1-ethyl-3-methylimidazolium chloride [EMIM][Cl] ionic liquid. Glassy carbon (GC) served as working electrode. The standard electrochemical techniques, such as cyclic voltammetry(CV), linear sweep voltammetry(LSV), chronopotentiometry(CP) and chronoamperometry(CP) were used under rotating and stationary conditions, at standard 100C. CV revealed two cathodic (C1 and C2) and two anodic (A1 and A2) current peaks. We are proposing that both cathodic current peaks belong to the same reduction of PdCl42− reaction, split into two by electrode surface morphology changes; C1 and C2 representing electroreduction of Pd on GC and Pd on Pd, respectively. The first anodic current peak (A1) is not well understood, but the second (A2) clearly distinguishes electrodissolution of Pd with thin film geometry. According to Levich and Levich-Koutecky analysis the first reduction step (C1) is the mixed kinetics, while the second (C2) is the mass transfer controlled. Diffusion coefficients estimated are of ~10−7cm2/s order. Concerning the stages of nucleation and growth of Pd, for the nucleation stage a 2D-instantatneous nucleation mechanism is proposed. The growth is aggregative, made of numerous Pd nanoclusters, consequently not fitting any of the 2D and 3D-growth models.

The paper presents a series of studies into the physicochemical properties such as density, viscosity and conductivity of acidic AlCl3–1-ethyl-3-methylimidazolium chloride ionic liquid (IL) at 30 °C. The ionic composition of the electrolyte is characterised by Raman spectroscopy. A study of the dependence of the ionic liquid specific conductivity on the concentration of AlCl3 at 0.50 ≤ xAl ≤ 0.67 (xAl is the mole fraction of AlCl3 in the melt) is undertaken. The plot of IL specific conductivity vs AlCl3 concentration smoothly decreases and does not contain any maxima across the investigated range of AlCl3 concentrations. A method of evaluating the transport numbers of chloroaluminate anions using only experimental data on conductivity, without performing additional experiments is proposed. A decrease in molar conductivity with the growth of AlCl3 concentration is found to be related to the decreasing total molar concentration of ions participating in charge carrying and the decreasing molar volume of the IL.

The effects of additives, such as 4-pyridinecarboxylic acid hydrazide (4-PCAH) and its analogs, and organic solvents, such as toluene, benzene and xylene, on the brightness of aluminum (Al) prepared using constant-current deposition from an ionic liquid of ethyl-3-methylimidazolium chloride (EMIC)-aluminum chloride (AlCl 3 ) were investigated by light spectroscopy, scanning electron microscopy (SEM), reflectivity tests, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy. In order for the deposited Al films to exhibit high brightness, a combined use of 4-PCAH and toluene is effective. Moreover, the relationship between the brightness ( i.e. , reflectance) of the prepared Al films and the molecular structure of a variety of additives was clarified. Both a pyridine ring and an acetyl hydrazine group are necessary for constituting an effective additive. The structural isomers of a given additive bring about different surface brightness, e.g., for PCAHs the reflectance at 450 nm is in the order of para -isomer > meta -isomer > ortho -isomer. It was considered that in 4-PCAH electron-withdrawing acetyl hydrazine group is bounded to the pyridine ring, and consequently the electron density around the nitrogen atom in the pyridine ring is decreased, which is conducive to the adsorption of 4-PCAH on the cathode of deposited Al films. In addition, the reflectance was found to increase with decreasing the crystalline domain size of Al deposits and with increasing the reaction resistance for Al electrodeposition. The reaction mechanism of Al electrodeposition from the present ionic liquid media containing various additives is also discussed briefly.

Pretreating biomass using ionic liquids (ILs) can decrease cellulose crystallinity and lead to improved hydrolysis. However, cellulase activity is often reduced in even low concentrations of ILs, necessitating complete washing between pretreatment and hydrolysis steps. To better understand how ILs interact with enzymes at the molecular scale, endoglucanase E1 from Acidothermus cellulolyticus was simulated in aqueous 1-ethyl-3-methylimidazolium chloride ([Emim]Cl). Homologs with differing surface charge were also simulated to assess the role of electrostatic interactions between the enzyme and the surrounding solvent. Chloride anions interacted with the enzyme surface via Coulomb or hydrogen bond interactions, while [Emim] cations primarily formed hydrophobic or ring stacking interactions. Cations strongly associated with the binding pocket of E1, potentially inhibiting the binding of substrate molecules. At elevated temperatures, cations also disrupted native hydrophobic contacts and caused some loss of secondary structure. These observations suggested that both cations and anions could influence enzyme behavior and that denaturing and inhibitory interactions might both be important in aqueous IL systems.

A double counter electrode electrodeposition system was developed to enable co-electrodeposition of Al and Zn with a desired composition. This system switches the active counter electrodes of different metals as a metal ion source to alter the composition of an EMIC–AlCl 3 -based ionic liquid bath. Using an integrated counter electrode composed of Al and Zn plates and a thin electrolyte cell, Al and Zn were co-electrodeposited on a Cu plate substrate by the galvanostatic pulse method. The effects of electrodeposition current density, distance between the working and counter electrodes, and electric charge ratio of anodic dissolution on the Al and Zn counter electrodes on the composition of coatings were examined. Experimental results confirmed that current density and charge ratio affected the composition of the coatings. On the other hand, the distance between the counter and the working electrode showed a rather complicated effect on the coating composition. This was explained by the transition of the transport mechanism of Zn ions supplied from the Zn counter electrode to the working electrode surface via the ionic liquid bath depending on the distance.

The anodic dissolution of aluminum metal was investigated in the Lewis acidic chloroaluminate ionic liquid, aluminum chloride-1-ethyl-3-methylimidazolium chloride. The investigation was conducted on aluminum rotating disk electrodes as a function of potential, ionic liquid composition, and temperature. Two different dissolution mechanisms were realized. At modest overpotentials, dissolution takes place under mixed kinetic-mass transport control. However, as the overpotential is increased to induce higher dissolution rates and/or the ionic liquid is made more acidic, the dissolution reaction transitions to a potential-independent passivation-like process ascribed to the formation of a porous solid layer of AlCl3(s). At a fixed temperature and composition, the limiting passivation current density displays Levich behavior and also scales linearly with the concentration of AlCl4- in the ionic liquid. The heterogeneous kinetics of the Al dissolution reaction were measured in the active dissolution potential regime. The exchange current densities were independent of the composition of the ionic liquid, and the anodic transfer coefficients were close to zero and seemed to be independent of the Al grain size.

The chemical changes in various morphological regions of Japanese beech (Fagus crenata) upon treatment with the ionic liquid 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which preferentially dissolves cellulose, have been investigated by Raman microscopy. The reactivity of polysaccharides and lignin with [C2mim][Cl] differed depending on the types of wood tissues. Chemical components in parenchyma cells showed higher resistance to degradation upon [C2mim][Cl] treatment than wood fiber and vessel. In addition, the lignin structure was partially degraded or modified by [C2mim][Cl] treatment, and its binding mode was complicated; nevertheless, lignin was stable in [C2mim][Cl].

The ever popular AlCl3-1-ethyl-3-ethylimidazolium chloride (EtMeImCl) ionic liquid (IL) system offers a unique solvation environment for many metal ions. In fact, the use of these chloroaluminate ionic liquids for the electrochemical surface finishing of metals was recently reviewed.1 These ionic liquids display adjustable Lewis acidity that depends directly on the mole ratio of the AlCl3 to the organic salt. The basic AlCl3-EtMeImCl mixture, which contains coordinately unsaturated Cl-, provides a solvation environment similar to aqueous HCl and NaCl, except of course without the complications due to the H2O solvent or H3O+. The opposite situation prevails in the Lewis acidic ionic liquid because the main chemically active ionic component of the ionic liquid is the coordinately unsaturated species, [Al2Cl7]-. Thus, there are no “hard” ligands available to form stable, isolable anionic complexes with the anodization product. Recently, both composition regions of the AlCl3-EtMeImCl IL system have been explored for the electrodissolution/electropolishing of Al.2 The advantages afforded by anodic dissolution of metals in this ionic liquid relative the aqueous acids and salt solutions commonly used for this purpose are quite obvious, i.e., the avoidance of the oxide surface films that invariably complicate the metal electropolishing process. In this paper, we report the thermodynamics and kinetics of the anodic dissolution of copper metal in the acidic and basic compositions of the AlCl3-EtMeImCl ionic liquid. In the former, the dissolution of copper at a Cu-RDE exhibits mixed control. No limiting current or passivation due to the formation of an insoluble surface film was apparent. In the basic composition region, mixed control was observed at small overpotentials, but as the overpotential was increased, a limiting current was obtained that scaled linearly with the Cl- concentration in the ionic liquid. The connection between these results and the mechanism of the dissolution process will be discussed. ____________________________________________ 1. T. Tsuda, G. R. Stafford and C. L. Hussey, J. Electrochem. Soc., 164, H5007 (2017). 2. C. Wang and C. L. Hussey, J. Electrochem. Soc., 163, H1186 (2015).

Development of eco-friendly materials for the removal of SO2 is a significant topic in sustainable chemical engineering process. In this work, we describe an efficient protocol for highly efficient and reversible SO2 capture by deep eutectic solvents (DESs) consisting of 1-ethyl-3-methylimidazolium chloride (EmimCl) and glycerol derivatives. The presented DESs exhibit an equal or much higher absorption capacity than previously reported DESs or ionic liquids in the same conditions. Particularly, EmimCl-glycerol (molar ratio 2:1) shows excellent reversible absorption through physical interactions supporting by FTIR and NMR spectroscopic experiments, thus presenting good potential as a candidate absorbent for the removal of SO2.

Mjerene su gustoće umjereno razrijeđenih otopina 1-etil-3-metilimidazolijevog klorida ( EMImCl )u metanolu pri različitim temperaturama, ϴ = 15, 20, 25, 30, i 35 ̊C. Iz dobivenih gustoća, određena su volumetrijska svojstva (prividni i parcijalni molarni volumeni) EMImCl u metanolu. Prividni granični molarni volumen i interakcijski koeficijent izračunati su korištenjem Massonove jednadžbe . Iz prividnog graničnog molarnog volumena, određenog pri različitim temperaturama, izračunata je prividna granična molarna ekspanzibilnost za EMImCl u metanolu pri svim radnim temperaturama. Dobiveni podaci dali su uvid u svojstva EMImCl u metanolu. The densities of moderately dilute solutions of the 1-ethly-3-methylimidazolium chloride (EMImCl) in methanol were measured (using Anton-Paar DMA 4500M densimeter) at diferent temperatures, ϴ= 15, 20, 25, 30 and 35 ̊C. From the obtained density data, volumetric properties (apparent molar volumes and partial molar volumes) have been evaluated. The volumetric data have been analyzed using Masson's equation. The limiting apparent molar volume or partial molar volume at infinite dilution, and the slope of Masson's equation at different temperatures for EMImCl in methanol have been interpreted in terms of ionion and ion-solvent interactions, respectively. In addition, negative values in the whole temperature range for the limiting apparent molar expansibility indicates structure breaking properties of EMImCl in methanol.

Rheological properties of cellulose solutions in 1-ethyl-3-methylimidazolium chloride/dimethyl sulfoxide ([Emim]Cl/DMSO, 7/3, w/w) in a wide range of concentration and temperature were investigated. The viscosity of cellulose/[Emim]Cl/DMSO solution agrees well with the complex viscosity suggesting Cox-Merz law is valid for the solution. The viscosity contributed by cellulose (eta (0)-eta (s) ) and cellulose concentration (c) scales as (eta (0)-eta (s) )similar to c (n) with n in the range of 2.00-1.57 and 4.52-3.79 in semidilute unentangled and semidilute entangled regimes, respectively, in the temperature of 25-100 A degrees C. Intrinsic viscosity of the solutions remains constant at temperature below 60 A degrees C and decreases linearly with the increase of temperature above 60 A degrees C. The activation energy of cellulose/[Emim]Cl/DMSO solution increases with the increase in cellulose concentration. The chain dynamics of cellulose in [Emim]Cl/DMSO follows Zimm model and Rouse model in dilute regime (lower than 0.5 wt%) and semidilute unentangled regime (between 0.5 and 2 wt%), respectively.