Ionic liquids which are often classified as low melting point salts have received significant attention from research groups and industries to be used in a wide range of applications. Many of these applications require thorough knowledge on the thermophysical properties of the ionic liquids before utilizing their full potentials in various fields. In this work, a series of alkylammonium cation and carboxylate anion-based room temperature protic ionic liquids (PILs) were synthesized by varying length of alkyl chain of the cation from diethyl to dibutyl combined with pentanoate, hexanoate and heptanoate anions. These ammonium-based PILs named as diethylammonium pentanoate [DEA][C5], diethylammonium hexanoate [DEA][C6], diethylammonium heptanoate [DEA][C7], dibutylammonium pentanoate [DBA][C5], dibutylammonium hexanoate [DBA][C6] and dibutylammonium heptanoate [DBA][C7] were characterized using Nuclear Magnetic Resonance (NMR) spectroscopy. The thermophysical properties of the PILs namely density, dynamic viscosity and refractive index were measured and analyzed. Density, ρ and dynamic viscosity, η were determined at T = (293.15 to 363.15) K and refractive index, nD was measured at T = (293.15 to 333.15) K. The fitting parameters are proposed for the empirical correlations of density, dynamic viscosity and refractive index. The values of thermal expansion coefficient, αp, molecular volume, Vm, standard entropy, S° and lattice potential energy, Upot also have been calculated by using the specified equations. The thermal decomposition temperature, Td was also determined using a thermogravimetric analyzer (TGA) while the differential scanning calorimetry (DSC) technique provided the glass transition, Tg, melting point, Tm and crystallization, Tc temperatures of the PILs. The experimental results revealed that the dependency of the experimental values namely the ρ, η, nD, and Td on the alkyl chain of the anion, size of the cations and the temperature of measurement.
Due to the substantial usage of fossil fuels, the utilization of lignocellulosic biomass as renewable sources for fuels and chemical production has been widely explored. The dissolution of lignocellulosic biomass in proper solvents is vital prior to the extraction of its important constituents, and ionic liquids (ILs) have been found to be efficient solvents for biomass dissolution. However, the high viscosity of ILs limits the dissolution process. Therefore, with the aim to enhance the dissolution of lignocellulosic biomass, a series of new ether-functionalized ILs with low viscosity values were synthesized and characterized. Their properties, such as density, viscosity and thermal stability, were analyzed and discussed in comparison with a common commercial IL, namely 1-butyl-3-methylimidazolium chloride (BMIMCl). The presence of the ether group in the new ILs reduces the viscosity of the ILs to some appreciable extent in comparison to BMIMCl. 1-2(methoxyethyl)-3-methylimidazolium chloride (MOE-MImCl), which possesses the lowest viscosity value among the other ether-functionalized ILs, demonstrates an ability to be a powerful solvent in the application of biomass dissolution via the sonication method. In addition, an optimization study employing response surface methodology (RSM) was carried out in order to obtain the optimum conditions for maximum dissolution of biomass in the solvents. Results suggested that the maximum biomass dissolution can be achieved by using 3 weight% of initial biomass loading with 40% amplitude of sonication at 32.23 min of sonication period.
Ionic liquids, which are extensively known as low-melting-point salts, have received significant attention as the promising solvent for CO2 capture. This work presents the synthesis, thermophysical properties and the CO2 absorption of a series of ammonium cations coupled with carboxylate anions producing ammonium-based protic ionic liquids (PILs), namely 2-ethylhexylammonium pentanoate ([EHA][C5]), 2-ethylhexylammonium hexanoate ([EHA][C6]), 2-ethylhexylammonium heptanoate ([EHA][C7]), bis-(2-ethylhexyl)ammonium pentanoate ([BEHA][C5]), bis-(2-ethylhexyl)ammonium hexanoate ([BEHA][C6]) and bis-(2-ethylhexyl)ammonium heptanoate ([BEHA][C7]). The chemical structures of the PILs were confirmed by using Nuclear Magnetic Resonance (NMR) spectroscopy while the density (ρ) and the dynamic viscosity (η) of the PILs were determined and analyzed in a range from 293.15K up to 363.15K. The refractive index (nD) was also measured at T = (293.15 to 333.15) K. Thermal analyses conducted via a thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) indicated that all PILs have the thermal decomposition temperature, Td of greater than 416K and the presence of glass transition, Tg was detected in each PIL. The CO2 absorption of the PILs was studied up to 29 bar at 298.15 K and the experimental results showed that [BEHA][C7] had the highest CO2 absorption with 0.78 mol at 29 bar. The CO2 absorption values increase in the order of [C5] < [C6] < [C7] anion regardless of the nature of the cation.
This work presents an in-depth kinetic thermal degradation comparison between traditional monocationic and the newly developed dicationic ionic liquid (IL), both coupled with a bromide (Br−) anion by using non-isothermal thermogravimetric analysis. Thermal analyses of 1-butyl-1-methylpyrrolidinium bromide [C4MPyr][Br] and 1,4-bis(1-methylpyrrolidinium-1-yl)butane dibromide [BisC4MPyr][Br2] were conducted at a temperature range of 50–650 °C and subjected to various heating rates, which are 5, 10, 15, 20 and 25 °C/min. Thermogravimetric analysis revealed that dicationic IL, [BisC4MPyr][Br2] is less thermally stable compared to monocationic [C4MPyr][Br]. A detailed analysis of kinetic parameters, which are the activation energy (Ea) and pre-exponential factor (log A), was calculated by using Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO) and Starink. This study revealed that the average Ea and log A of [BisC4MPyr][Br2] are lower than [C4MPyr][Br], which may be contributed to by its low thermal stability. Conclusively, it proved that the Ea and log A of ILs are strongly related to the thermal stability of ILs.
The special features of metal–organic frameworks (MOFs), namely, tunable porosity, exceptional structure, high surface area and high adsorption capability enable them to be widely studied in many applications including carbon capture and storage (CCS), biomedical engineering, catalysis and pollutant treatment. Despite these remarkable properties, MOFs are known to be moisture-sensitive, hardly recyclable and expensive in fabrication cost which limits their breakthrough performance in more efficient uses. Recently, extensive studies have been devoted to counter those shortcomings by embedding MOFs with support materials using various series of synthetic designs to yield incorporated MOF hybrid materials to counter their limitations. In view of this interest, this review summarizes the latest developments of incorporated MOFs with various materials, namely, ionic liquids (ILs), membranes and metal species. Pre-synthetic and post-synthetic synthesis methods are also discussed. This review also aims to highlight the factors associated with incorporated MOF performance such as materials selection and mass ratio which could have favorable effects in gas separation, catalysis and wastewater treatment applications. The data indicate that incorporated MOF hybrid materials exhibit exceptional properties including excellent robustness and stability. Correspondingly, in comparison to pristine MOFs, incorporated MOF hybrid materials significantly improve, among others, the gas selectivity, catalyst activity and dye removal efficiency in gas separation, catalysis and wastewater treatment, respectively. In addition, the challenge related to the utilization of this newly incorporated material is mentioned.
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