RESUMEN
Systematic analyses of electrolyte physicochemical properties are important to screen ionic liquids (ILs) and understand the electrochemical performance of supercapacitor electrolytes. This study harmonizes the evaluation of electrochemical performance and transport properties of eight shortlisted ILs from 22 commercially available hydrophobic ILs toward achieving a ≥ 5 V supercapacitor capable of high-temperature operation (up to 353.15 K). The eight ILs are N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Pyr 1, 3] [TFSI], N-Pentyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([Pyr 1, 5] [TFSI]), N-Propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([Pyr 1, 3] [FSI]), 1-Methyl-1-(2-methoxyethyl)pyrrolidinium Bis(trifluoromethanesulfonyl)imide ([Pyr 1, 102] [TFSI]), 1-Methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide ([Pip 1, 3] [TFSI]), 1-Methyl-1-propylpiperidinium bis(fluorosulfonyl)imide ([Pip 1, 3] [FSI]), N-Trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide ([N 111, 3] [TFSI]), N-Trimethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide ([N 111, 6] [TFSI]). The density, viscosity, and ionic conductivity of the eight ILs were measured between 278.15 and 373.15 K to confirm the effects of temperature and ion structure before electrochemical characterization. The [FSI]-based ILs ([Pip 1, 3] [FSI] and [Pyr 1, 3] [FSI]) showed lower densities and viscosities compared to other ILs among the eight based on [TFSI]. Consequently, the highest conductivity was obtained for [Pyr 1, 3] [FSI]. Cyclic voltammetry and impedance spectroscopy was performed on supercapacitors assembled with the eight ILs as electrolytes between 298.15-353.15 K. Conclusion from the two-electrode supercapacitors using multi-walled carbon nanotubes showed the 6 most-applicable ILs towards the targeted ≥ 5 V SC at high temperature are [Pip 1, 3] [TFSI] (5.4 V), [Pip 1, 3] [FSI] (5 V), [N 111, 3] [TFSI] (5.1 V), [N 111, 6] [TFSI] (5.2 V), [Pyr 1, 102] [TFSI] (5.2 V), and [Pyr 1, 5] [TFSI] (5.2 V).
RESUMEN
Ionic liquids (ILs) show remarkable performance in enhancing the naphthenic acid extraction efficiency and decreasing the extraction time. However, the ultrasonic-assisted IL-based extraction of naphthenic acid is merely addressed previously. Therefore, this study investigated the impact of essential ultrasonic parameters, including amplitude and time, on naphthenic acid extraction using different ILs, and the system was optimized for maximum extraction. The IL 1,8-diazobicyclo[5.4.0]-undec-7-ene (DBU) with thiocyanate anions revealed the highest efficiency in extracting naphthenic acid from a model oil (dodecane) at optimized conditions, and the experimental liquid-liquid equilibrium data were obtained at atmospheric pressure for the mixture of dodecane, [DBU], thiocyanate, and naphthenic acid. In addition, the influence of the chain length of the cation (hexyl, octyl, or decyl) on the extraction efficiency was also evaluated by determining the distribution coefficients, and the conductor-like screening model for real solvents (COSMO-RS) study was carried out at infinite dilution. It was found that [DBU-Dec] [SCN] gives the best extraction efficiency and has a distribution coefficient of 9.2707 and a performance index of 49.48. Based on these values, ILs can be ordered as follows: [DBU-Dec] [SCN] > [DBU-Oct][SCN] > [DBU-Hex][SCN] in the decreasing order of performance index 49.48, 41.58, and 28.13. Moreover, non-random two liquid and Margules thermodynamic models were employed to investigate the interaction parameters between the components. Both models showed excellent agreement with the experimental results and could successfully be used for ultrasonic-assisted IL extraction of naphthenic acid.
RESUMEN
The electrochemical stability of 22 commercially available hydrophobic ionic liquids was measured at different temperatures (288.15, 298.15, 313.15, 333.15 and 358.15 K), to systematically investigate ionic liquids towards electrolytes for supercapacitors in harsh weather conditions. Bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)imide anions in combination with 1-Butyl-1-methylpyrrolidinium, 1-Ethyl-3-methylimidazolium, N-Ethyl-N, N-dimethyl-N(2methoxyethyl)ammonium, 1-Methyl-1-(2-methoxyethyl)pyrrolidinium, N-Pentyl-N-methylpyrrolidinium, N, N-Diethyl-N-methyl-N-propylammonium, N, N-Dimethyl-N-ethyl-N-benzyl ammonium, N, N-Dimethyl-N-Ethyl-N-phenylethylammonium, N-Butyl-N-methylpiperidinium, 1-Methyl-1-propylpiperidinium, N-Tributyl-N-methylammonium, N-Trimethyl-N-butylammonium, N-Trimethyl-N-butylammonium, N-Trimethyl-N-propylammonium, N-Propyl-N-methylpyrrolidinium cations were selected for the study. Linear regression with a numerical model was used in combination with voltammetry experiments to deduce the temperature sensitivity of both anodic and cathodic potential limits (defining the electrochemical stability window), in addition to extrapolating results to 283.15 and 363.15 K. We evaluated the influence of the cations, anions, and the presence of functional groups on the observed electrochemical stability window which ranged from 4.1 to 6.1 V.
RESUMEN
Alkaline ionic liquids (ILs) with unconventional organic anions were prepared and used for cellulose dissolution studies. High concentrations of cellulose were dissolved at room temperature in the phenolate based imidazolium IL [C2mim][OPh], combined with organic solvent, and up to 45 wt-% cellulose dissolution (wt-% MCC of weight IL) was readily achieved at 100⯺C. No functionalization of the regenerated cellulose was observed during the dissolution process (FTIR). Characteristic cellulose II XRD diffraction pattern was observed after IL dissolution and regeneration of MCC. The crystallinity index (CI) of the pretreated MCC was reduced from 93.2 % to 31 %. Inert conditions were not required for the cellulose dissolution experiments. This study indicates that the IL H-bond basicity is not the only key parameter determining their cellulose dissolution ability. The alkaline ILs represent an energy efficient and sustainable approach for cellulose dissolution.
RESUMEN
Structurally modified hydroxyl functionalized pyridinium ionic liquids (ILs), liquid at room temperature, were synthesized and characterized. Alkylated N-(2-hydroxyethyl)-pyridinium ILs were prepared from alkylpyridines via corresponding bromide salts by N-alkylation (65-93%) and final anion exchange (75-96%). Pyridinium-alkylation strongly influenced the IL physicochemical and electrochemical properties. Experimental values for the ILs physicochemical properties (density, viscosity, conductivity, and thermal decomposition temperature), were in good agreement with corresponding predicted values obtained by theoretical calculations. The pyridinium ILs have electrochemical window of 3.0-5.4 V and were thermally stable up to 405°C. The IL viscosity and density were measured over a wide temperature range (25-80°C). Pyridine alkyl-substitution strongly affected the partial positive charge on the nitrogen atom of the pyridinium cations, as shown by charge distribution calculations. On-going studies on Mg complexes of the new ILs demonstrate promising properties for high current density electrodeposition of magnesium.
RESUMEN
The use of ionic liquids (ILs) in applications ranging from catalysis to reaction media in organic synthesis has been successfully demonstrated in several cases. For any given IL application, fundamental properties, such as viscosity, thermal stability, and toxicity have to be considered. Another property of interest is the polarity, which is a crucial indicator of solvent effects on chemical processes. Given the near-infinite combinations of cations and anions, experimental determination of solvatochromic parameters, such as the hydrogen-bond acidity and basicity, and dipolarity-polarizability is prohibitive. To address this, we evaluate the utility of alternative schemes based on parameters derived from COSMO-RS (COnductor-like Screening MOdel for Real Solvents) computations. The scheme is applied to a large library of yet-to-be-synthesized ionic liquids, to identify promising candidates for applications in biomass dissolution.
RESUMEN
Magnesium(ii) complexes, [Mg2+(hfac-)3][Cation+], were prepared as solids from hydrophobic hexafluoroacetylacetonate ionic liquids ([Cation+][hfac-] ILs) and Mg(Tf2N)2. 1-Butyl-3-methylimidazolium ([C4mim]), N-butylpyridinium ([C4Pyr]), N-butyl-N-methylpiperidinium ([C4Pip]), N-hexyl-N-methylmorpholinium ([C6Morp]) and N-butyl-N-methylpyrrolidinium ([C4pyrr]) were used as cationic cores. The [C4Pip][hfac], [C4Pyr][hfac] and [C6Morp][hfac] ILs were prepared for the first time. New Mg(ii) complexes, [C4mim][Mg(hfac)3], [C4Pip][Mg(hfac)3], [C4Pyr][Mg(hfac)3], [C6Morp][Mg(hfac)3] and [C4Pyrr][Mg(hfac)3], were obtained from the [hfac] based ILs. The crystal structures of the novel Mg(ii) complexes show the coordination of three [hfac] anions to the Mg2+ ion through the two oxygen atoms of each [hfac] anion.
RESUMEN
The electrical conductivity of a series of pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids, functionalized with a nitrile (cyano) group at the end of an alkyl chain attached to the cation, was studied in the temperature range between 173 K and 393 K. The glass formation of the ionic liquids is influenced by the length of the alkyl spacer separating the nitrile function from the pyrrolidinium ring. The electrical conductivity and the viscosity do not show a monotonic dependence on the alkyl spacer length, but rather an odd-even effect. An explanation for this behavior is given, including the potential energy landscape picture for the glass transition.
RESUMEN
Two series of 1-alkylpyridinium and N-alkyl-N-methylpiperidinium ionic liquids functionalized with a nitrile group at the end of the alkyl chain have been synthesized. Structural modifications include a change of the alkyl spacer length between the nitrile group and the heterocycle of the cationic core, as well as adding methyl or ethyl substituents on different positions of the pyridinium ring. The anions are the bromide and the bis(trifluoromethylsulfonyl)imide ion. All the bis(trifluoromethylsulfonyl)imide salts as well as the bromide salts with a long alkyl spacer were obtained as viscous liquids at room temperature, but some turned out to be supercooled liquids. In addition, pyrrolidinium and piperidinium ionic liquids with two nitrile functions attached to the heterocyclic core have been prepared. The crystal structures of seven pyridinium bis(trifluoromethylsulfonyl)imide salts are reported. Quantum chemical calculations have been performed on model cations and ion pairs with the bis(trifluoromethylsulfonyl)imide anion. A continuum model has been used to take solvation effects into account. These calculations show that the natural partial charge on the nitrogen atom of the nitrile group becomes more negative when the length of the alkyl spacer between the nitrile functional group and the heterocyclic core of the cation is increased. Methyl or methoxy substituents on the pyridinium ring slightly increase the negative charge on the nitrile nitrogen atom due to their electron-donating abilities. The position of the substituent (ortho, meta, or para) has only a very minor effect on the charge of the nitrogen atom. The (15)N NMR spectra of the bis(trifluoromethylsulfonyl)imide ionic liquids were recorded with the nitrogen-15 nucleus at its natural abundance. The chemical shift of the (15)N nucleus of the nitrile nitrogen atom could be correlated with the calculated negative partial charge on the nitrogen atom.