Physical and electrochemical properties of lithium-doped 1-butyl-3-methylimidazolium salts

Two well known room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]) and 1-butyl-3-methylimidazolium iodide ([BMIm][I]), were synthesized. Their physical properties such as reflective indices, densities, viscosities, heat capacities, and heats of dilution were measured. The overall properties of [BMIm][BF₄] obtained after two-step reactions were superior to those of the IL with a halide anion. The incorporation of lithium ions using lithium tetrafluoroborate (LiBF₄) in each IL was carried out and ionic conductivities as a function of temperature and Li ion concentration were investigated. The isothermal conductivity graph showed a parabolic curve shape suggesting that the maximum values exist at a specific concentration condition while they continuously increased as the temperature increased. The conductivities reached as high as 10⁻³ S·cm⁻¹.     

Surface tension and viscosity of 1-butyl-3-methylimidazolium iodide and 1-butyl-3-methylimidazolium tetrafluoroborate, and solubility of lithium bromide+1-butyl-3-methylimidazolium bromide in water

The surface tension and viscosity of 1-butyl-3-methylimidazolium iodide ([bmim][I]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) were measured over a temperature range of 298. 15 to 323.15 K. It was found that both the viscosity and surface tension decrease with increasing temperature and that the surface tension and viscosity values of [bmim][I] were higher than those of [bmim][BF₄]. Additionally, the solubility of lithium bromide (2)+1-butyl-3-methylimidazolium bromide ([bmim][Br]) (3) in water (1) was measured at three different mass ratios (w₂/w₃=4 and 7, w₃=0) by using a visual polythermal method. The solubility of the suggested systems was better than that of lithium bromide in water.     

Preparation of colloidal silver nanoparticles by chemical reduction method

Colloidal silver nanoparticles were obtained by chemical reduction of silver nitrate in water with sodium borohydride (NaBH₄) in the presence of sodium dodecyl sulfate (SDS) as a stabilizer. The obtained nanoparticles were characterized by their UV-vis absorption spectra and transmission electron micrograph (TEM) images. The UV-vis absorption spectra showed that NaBH₄ served not only as a reducing agent but also as a stabilizer, which protects the aggregation of silver nanoparticles. The TEM images showed that the particles were dispersed better with increasing the NaBH₄ concentration.     

Electrodeposition of nanocrystalline silver films and nanowires from the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate

We report in this paper on the electrodeposition of nanocrystalline silver films and nanowires in the air and water stable ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate [EMIm]TfO containing Ag(TfO) as a source of silver. The study was performed by means of cyclic voltammetry and chronoamperometry, and the electrodeposits were characterized by SEM-EDX and XRD. The cyclic voltammetry behaviour showed typical reduction and oxidation peaks corresponding to the deposition and stripping of silver in the employed electrolyte. XRD patterns of the electrodeposited silver layers revealed the characteristic peaks of crystalline silver with crystallites in the nanosize regime. Silver nanowires with average diameters and lengths of about 200 nm and 3 μm, respectively, were prepared by potentiostatic deposition within a commercial nuclear track-etched polycarbonate template.     

Physical and electrochemical properties of 1-(2-hydroxyethyl)-3-methyl imidazolium and N-(2-hydroxyethyl)-N-methyl morpholinium ionic liquids

Various ionic liquids (ILs) were prepared via metathesis reaction from two kinds of 1-(2-hydroxyethyl)-3-methyl imidazolium ([HEMIm]⁺) and N-(2-hydroxyethyl)-N-methyl morphorinium ([HEMMor]⁺) cations and three kinds of tetrafluoroborate ([BF₄]⁻), bis(trifluoromethanesulfonyl)imide ([TFSI]⁻) and hexafluorophosphate ([PF₆]⁻) anions. All the [HEMIm]⁺ derivatives were in a liquid state at room temperature. In particular, [HEMIm][BF₄] and [HEMIm][TFSI] showed no possible melting point from −150 °C to 200 °C by DSC analysis, and their high thermal stability until 380-400 °C was verified by TGA analysis. Also, their stable electrochemical property (electrochemical window of more than 6.0 V) and high ionic conductivity (0.002-0.004 S cm⁻¹) further confirm that the suggested ILs are potential electrolytes for use in electrochemical devices. Simultaneously, the [HEMMor]⁺ derivatives have practical value in electrolyte applications because of their easy synthesis procedures, cheap morpholinium cation sources and possibilities of high Li⁺ mobility by oxygen group in the morpholinium cation. However, [HEMMor]⁺ derivatives showing high viscosity usually had lower ionic conductivities than [HEMIm]⁺ derivatives.     

Electrodeposition of palladium–silver in a Lewis basic 1-ethyl-3-methylimidazolium chloride-tetrafluoroborate ionic liquid

The electrodeposition of palladium–silver alloys was investigated in a basic 1-ethyl-3-methylimidazolium chloride/tetrafluoroborate ionic liquid containing Pd(II) and Ag(I). Cyclic voltammetry experiments showed that the reduction of Ag(I) occurs prior to the reduction Pd(II). Both electrodeposition processes require nucleation overpotential. Energy-dispersive spectroscopy data indicated that the composition of the Pd–Ag alloys could be varied by deposition potential and concentrations of Pd(II) and Ag(I) in the solution. The Pd content in the deposited Pd–Ag alloy increased with decreasing deposition potential and the Pd mole fraction in the plating bath. At potentials where the deposition of both Pd and Ag was mass-transport limited, the Pd/Ag ratio in the electrodeposited alloys was slightly less than the Pd(II)/Ag(I) ratio in the ionic liquid due to the smaller diffusion coefficient of Pd(II). Scanning electron micrographs of the electrodeposits showed that in general, the Pd–Ag alloys were nodular and become more compact upon increasing the temperature up to 120 °C.     

Diffusion coefficient of ferrocene in 1-butyl-3-methylimidazolium tetrafluoroborate - concentration dependence and solvent purity

The ionic liquid l-butyl-3-methylimidazolium tetrafluoroborate is used as electrolyte in the electrochemical determination of the diffusion coefficient of ferrocene as a function of concentration by cyclic voltammetry and chronoamperometry. An improved synthesis of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate is described, which yields a product of high purity suitable for electrochemical purposes. A qualitative color test is discussed which allows the simple detection of silver ion contaminations. The diffusion coefficient of ferrocene appears to be concentration dependent in the solvent chosen.     

Vapor pressure measurement and correlation of acetonitrile+1-butyl-3-methylimidazolium chloride,+1-butyl-3-methylimidazolium tetrafluoroborate,and+1-hexyl-3-methylimidazolium chloride

Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride ([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and+1-hexyl-3-methylimidazolium chloride ...     

Electrodeposition of palladium-indium from 1-ethyl-3-methylimidazolium chloride tetrafluoroborate ionic liquid

Voltammetry at a glassy carbon electrode was used to study the electrochemical co-deposition of Pd-In from a chloride-rich 1-ethyl-3-methylimidazolium chloride/tetrafluoroborate air-stable room temperature ionic liquid at 120 °C. Deposition of Pd alone occurs prior to the overpotential deposition (OPD) of bulk In. However, underpotential deposition (UPD) of In on the deposited Pd was observed at the potential same as the deposition of Pd. The UPD of In on Pd was, however, limited by a slow charge transfer rate. Samples of Pd-In alloy coatings were prepared on nickel substrates and characterized by energy dispersive spectroscope (EDS), scanning electron microscope (SEM) and X-ray powder diffraction (XRD). The electrodeposited alloy composition was relatively independent on the deposition potential within the In UPD range. At more negative potentials where the OPD of Pd-In has reached mass-transport limited region, the alloy composition corresponds to the Pd(II)/In(III) composition in the plating bath. The Pd-In alloy coatings obtained by direct deposition of Pd and UPD of In on the deposited Pd appeared to be superior to the Pd-In alloys that were obtained via the co-deposition of Pd and bulk In at OPD potentials.     

乙腈+[C4mim][Cl]、乙腈+[C4mim][BF4]、乙腈+[C6mim][Cl]的气液平衡测定与关联（英文）

Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride ([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and+1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]) at temperatures of 313 to 353 K by a quasi-static method. The experimental data for the binary sys-tems were correlated by the non-random two liquid (NRTL) equation with an average absolute relative deviation (AARD) of within 1.84%. The results indicate that the three ionic liquids (ILs) can result in a negative deviation from the Raoult's law for the binary solutions containing acetonitrile, and the affinity between ILs and acetonitrile mole-cules fol ows the order [C4mim][BF4]+acetonitrile N [C4mim][Cl]+acetonitrile N [C6mim][Cl]+acetonitrile.     

Influence of ionic liquid on graphite/silver nanoparticles dispersion and antibacterial properties against Escherichia coli of PP/EPDM composite coatings

In this work, graphite doped with silver nanoparticles are synthesized and coated onto a PP/EPDM blend surface. Three nanoparticles deposition methods are used. In one method, the nanoparticles are directly deposited on previously corona discharge-treated TPO surface. Another method is by compression deposition of nanoparticles in a thin layer forming a segregated coating. In the last method, a nanoparticle-polymer composite is deposited and then treated by corona discharge to expose the deposited nanoparticles. These last two methods show excellent antimicrobial activity (R = 2.8 and 3.9, respectively) and higher inhibition values (85% and 89%, respectively) against Escherichia coli strains. The effect of using HMIMPF6 and BMIMBF4 ionic liquids on particle dispersion and antibacterial activity against E. coli is evaluated. Using ionic liquids enhance the antibacterial activity (from R = 3.9 to 5.4) and inhibition rates (from 89% to 99.8%) of the samples. As a result, a thermoplastic elastomer (TPE) material with enhanced antibacterial properties against E. coli is obtained using ionic liquids, which offer significant promise as a material for medical applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48714.     

Electrodeposition of tin and antimony in 1-ethyl- 3-methylimidazolium tetrafluoroborate ionic liquid

The electrodepositions of Sn(II) and Sb(III) were studied in the [EMIm]BF₄ ionic liquid at ambient temperature. Linear sweep voltammetry (LSV) results indicated that the reductions of Sn(II) and Sb(III) on Pt electrode are electrochemically irreversible. The diffusion coefficients of Sn(II) and Sb(III) in the ionic liquid electrolyte were determined in terms of the LSV data. Tin and antimony ions form simpler Sn(II) chlorocomplex species and higher Sb(III) chlorocomplexes, respectively present in the ionic liquid electrolyte. Energy dispersive X-ray spectroscopy (EDX) analysis revealed that tin and antimony alloys can be electroplated in the ionic liquid electrolyte.     

Electrochemical aspects of black chromium electrodeposition from 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

The electrochemical behaviour of trivalent chromium (Cr³⁺) in 1-butyl-3-methylimidazolium tetrafluoroborate [BMIm][BF₄] ionic liquid solutions was studied by cyclic voltammetry and chronoamperometry. The reduction of Cr³⁺ occurs in two steps, Cr³⁺ to Cr²⁺ and Cr²⁺ to Cr⁰, respectively. The first step is quasi-reversible with a diffusion coefficient of Cr³⁺ in solution of 3.13 × 10⁻⁸ cm² s⁻¹ at 303 K and 25.8 × 10⁻⁸ cm² s⁻¹ at 358 K, estimated from cyclic voltammetry data.Black chromium films were electrodeposited on copper, stainless steel and carbon steel substrates at a constant potential of −1.5 V vs Pt quasi-reference electrode. The films consist of aggregates of nanosized particles. The coatings in the as-deposited condition present an amorphous structure but after annealing for 4 h, a nanocrystalline Cr₂O₃ phase is formed, with an average crystallite size of 17 nm.     

Poly(vinylidenefluoride)-hexafluoropropylene gel electrolytes based on N-(2-hydroxyethyl)-N-methyl morpholinium ionic liquids

Poly(vinylidenefluoride)-hexafluoropropylene (PVdF(HFP))-ionic liquid gel electrolytes were prepared by using ionic liquids based on N-(2-hydroxyethyl)-N-methyl morpholinium tetrafluoroborate and N-(2-hydroxyethyl)-N-methyl morpholinium hexafluorophosphate. TGA and FT-IR analyses confirmed that the solvent, N,N-dimethylacetamide (DMAC), used for mixing the PVdF(HFP) polymer with the ionic liquid, was almost totally removed during the gelling and drying processes. SEM photographs were taken of the surface structure of the PVdF(HFP)-ionic liquid in order to evaluate the morphology of the film’s surface according to the mixing ratio, as well as the nature of the ionic liquid. The thermal behaviors of PVdF(HFP)-ionic liquid gels were observed to be similar to those of neat ionic liquids through a DSC analysis, and the compatibility between the polymer and the ionic liquid was investigated by an XRD analysis. The ionic conductivities of all the gels were 10⁻⁴–10⁻⁸S·cm⁻¹ in a temperature range of 20°C to 70°C.     

液相化学还原法制备单分散的纳米银粒子

以月桂酸为修饰剂,水合肼为还原剂,银氨溶液为银源,在水相中利用液相化学还原法制备了单分散的粒径分布均匀的纳米银粒子。利用透射电子显微镜(TEM)、X射线衍射(XRD)对样品的形貌和结构进行了分析,研究表明,修饰剂与硝酸银的质量比、反应温度对纳米银形貌及粒径有很大影响。当修饰剂与硝酸银的质量比为1.2∶1、反应温度为室温时,能够制备平均粒径为8 nm、粒径均匀、单分散的纳米银粒子。另外,UV光谱也证实,所制的溶胶为粒径均匀的纳米银溶胶。     

High-pressure phase behavior of carbon dioxide in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Phase equilibrium data of carbon dioxide in the ionic liquid 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]) are presented at high pressures up to about 30 MPa and at temperatures between 298.15 K and 343.15 K. The solubilities at a given temperature were determined by measuring the bubble point pressure of the ionic liquid solution with carbon dioxide dissolved using the high-pressure equilibrium apparatus equipped with a variable-volume view cell. Solubility results are reported for carbon dioxide concentrations ranging from 0.21 up to 0.80 mole fraction. Carbon dioxide gave very high solubilities in the ionic liquid at lower pressures, while the equilibrium pressure increased very steeply at higher concentrations of carbon dioxide. The solubility of carbon dioxide in the ionic liquid decreased with an increase in temperature.     

Formation of RuO2 nanoparticles by thermal decomposition of Ru(NO)(NO3)3

A simple one-pot synthesis of RuO₂ nanoparticles by the thermal decomposition of ruthenium nitrosyl nitrate [Ru(NO)(NO₃)₃] up to 800 °C was investigated. The RuO₂ phase was characterized by XRD, SAXS, FE SEM/EDS, Raman, DTA/TGA and FT-IR techniques. Broadening of prominent diffraction lines (110), (101) and (211) was used to estimate nanocrystallite sizes in RuO₂ particles. FE SEM showed the formation of RuO₂ plates at 400 °C which consisted of RuO₂ nanoparticles of about 15–25 nm in size. At 800 °C RuO₂ nanoparticles showed the sintering effect and some of them increased in size to about 200 nm. Raman and FT-IR spectra consolidated the findings. Moreover, DTA curves showed the decomposition and release of NO and NO₃⁻ groups to be a stepwise process.     

Electrochemical studies of four organometallic redox couples as possible reference redox systems in 1-ethyl-3-methylimidazolium tetrafluoroborate

The electrochemical behavior of four organometallic redox couples has been studied in the room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate. Diffusion controlled anodic and cathodic peaks were found for the redox couples Fc/Fc⁺ (ferrocene/ferrocenium), Cc/Cc⁺ (cobaltocene/cobaltocenium) on glassy carbon, platinum and gold. Bis(biphenyl)chromium(I) tetraphenylborate (BCr/BCr⁺) yielded a well-behaved diffusion controlled pair of cathodic-anodic peaks only on glassy carbon and gold as working electrodes. The electrode reaction of decamethylferrocene was affected by adsorption of the reduced form on all of the three working electrodes employed by us. The applicability of three of the four redox couples studied as candidates for reference redox systems in this ionic liquid is discussed.     

2,6-二甲氧基苯酚在1-丁基-3-甲基咪唑四氟硼酸盐水溶液中溶解行为的红外光谱分析

利用衰减全反射红外光谱(ATR-IR)和二维相关红外技术研究2, 6-二甲氧基苯酚(2, 6-DMP)在1-丁基-3-甲基咪唑四氟硼酸盐([C₄mim]BF₄)水溶液(离子液体摩尔分数x_IL=1.0～0.02)中的溶解行为。随着水量增大, 2, 6-DMP溶解度先增大而后急剧减小, 对应的x_IL阈值为0.1。2, 6-DMP与[C₄mim]BF₄之间存在强相互作用, 2, 6-DMP上的甲氧基是重要作用位点之一;当少量的水加入[C₄mim]BF₄(x_IL=0.1～1.0), 致密的离子簇结构被解离, 2, 6-DMP容易与[C₄mim]BF₄作用, 溶解度增大;随着大量水加入(0.02IL<0.1), 离子簇完全解离为大分子水簇包围的离子对, 憎水的2, 6-DMP与[C₄mim]BF₄作用困难, 溶解度减小。这种由于水量改变引起的[C₄mim]BF₄水溶液微观结构变化影响2, 6-DMP溶解行为。