Ionic-Liquid-Based Nanofluids and Their Heat-Transfer Applications: A Comprehensive Review

Due to the improved thermophysical characteristics of ionic liquids (ILs), such as their strong ionic conductivity, negligible vapor pressure, and thermal stability at high temperatures, they are being looked at viable contender for future heat transfer fluids. Additionally, the dispersing nanoparticles can further improve the thermophysical characteristics and thermal performance of ionic liquids, which is one of the emerging research interests to increase the heat transfer rates of the thermal devices. The latest investigations about the utilization of ionic liquid nanofluids as a heat transfer fluid is summarized in this work. These summaries are broken down into three types: (a) the thermophysical parameters including thermal conductivity, viscosity, density, and specific heat of ionic liquids (base fluids), (b) the thermophysical properties like thermal conductivity, viscosity, density, and viscosity of ionic liquids based nanofluids (IL nanofluids), and (iii) utilization of IL nanofluids as a heat transfer fluid in the thermal devices. The techniques for measuring the thermophysical characteristics and the synthesis of IL nanofluids are also covered. The suggestions for potential future research directions for IL nanofluids are summarized.     

Interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids with glucose in water: a study of volumetric properties, viscosity, conductivity and NMR

Extensive applications of ionic liquids (ILs) may result in their accumulation in the ecological environment and organisms. Although ILs are popularly called "green solvents", their toxicity, in fact, has been exhibited. Therefore the interaction of ILs with biomolecules is a cutting-edge research subject. Herein, the interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids ([C(4)mim][HCOO], [C(4)mim][CH(3)COO] and [C(4)mim][CH(3)CH(2)COO]) with glucose in water were studied for their volumetric properties, viscosity, conductivity and NMR spectra. Limiting apparent molar volumes (V(Φ, IL)(0)), viscosity B-coefficients, limiting molar conductivities (Λ(0)) and Walden products (Λ(0)η(0)) were evaluated for the ILs in glucose + water solutions. Volumetric interaction parameters were also obtained from the transfer volumes of the ionic liquids. The contributions of the solvent properties (B(1)) and the ionic liquid-solvent interactions (B(2)) to the B-coefficient were extracted, together with molar activation energies (Δμ(IL)(0≠)) of the ionic liquids for viscous flow of the aqueous glucose + IL solution. In addition, the (13)C and (1)H NMR spectra of methyl β-D-glucopyranoside and ILs in β-D-glucopyranoside + IL + D(2)O were studied. The NMR results show that no special and strong interactions were observed between glucopyranoside and the ILs. However, it was confirmed that the H2 on the imidazolium ring has more activity (acidity) than atoms H4 and H5. The macro-properties and their changes were also discussed in terms of the size, structure and solvation of the ILs and glucose.     

Computational studies of room temperature ionic liquid-water mixtures

Room temperature ionic liquids (IL) have been used in numerous applications in chemistry. Addition of water alters many of their properties making it possible to custom design solvents for specific applications. Along with experiments, computational studies using various approaches have provided key insights into the structure and dynamics of IL systems, as well as aggregate formation and phase behavior of the IL/water mixtures. These systems provide computational challenges since ILs and IL/water mixtures are viscous liquids with intrinsically slow processes and structural organization over surprisingly large length scales, which push the limits of applicability of the available techniques. Recent developments in the studies of IL/water mixtures using computational methodologies are reviewed and the future prospects for the field are briefly discussed.     

Ionic liquids: solvents and sorbents in sample preparation

The applications of ionic liquids (ILs) and IL‐derived sorbents are rapidly expanding. By careful selection of the cation and anion components, the physicochemical properties of ILs can be altered to meet the requirements of specific applications. Reports of IL solvents possessing high selectivity for specific analytes are numerous and continue to motivate the development of new IL‐based sample preparation methods that are faster, more selective, and environmentally benign compared to conventional organic solvents. The advantages of ILs have also been exploited in solid/polymer formats in which ordinarily nonspecific sorbents are functionalized with IL moieties in order to impart selectivity for an analyte or analyte class. Furthermore, new ILs that incorporate a paramagnetic component into the IL structure, known as magnetic ionic liquids (MILs), have emerged as useful solvents for bioanalytical applications. In this rapidly changing field, this Review focuses on the applications of ILs and IL‐based sorbents in sample preparation with a special emphasis on liquid phase extraction techniques using ILs and MILs, IL‐based solid‐phase extraction, ILs in mass spectrometry, and biological applications.     

Novel halogen-free chelated orthoborate-phosphonium ionic liquids: synthesis and tribophysical properties

We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel-aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.     

Influence of Substituents and Functional Groups on the Surface Composition of Ionic Liquids

We have performed a systematic study addressing the surface behavior of a variety of functionalized and non‐functionalized ionic liquids (ILs). From angle‐resolved X‐ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium‐based ILs methylated at the C2 position, a phenyl‐functionalized IL, an alkoxysilane‐functionalized IL, halo‐functionalized ILs, thioether‐functionalized ILs, and amine‐functionalized ILs. The results are compared with the results for corresponding non‐functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.     

Ionogels, ionic liquid based hybrid materials

The current interest in ionic liquids (ILs) is motivated by some unique properties, such as negligible vapour pressure, thermal stability and non-flammability, combined with high ionic conductivity and wide electrochemical stability window. However, for material applications, there is a challenging need for immobilizing ILs in solid devices, while keeping their specific properties. In this critical review, ionogels are presented as a new class of hybrid materials, in which the properties of the IL are hybridized with those of another component, which may be organic (low molecular weight gelator, (bio)polymer), inorganic (e.g. carbon nanotubes, silica etc.) or hybrid organic-inorganic (e.g. polymer and inorganic fillers). Actually, ILs act as structuring media during the formation of inorganic ionogels, their intrinsic organization and physicochemical properties influencing the building of the solid host network. Conversely, some effects of confinement can modify some properties of the guest IL, even though liquid-like dynamics and ion mobility are preserved. Ionogels, which keep the main properties of ILs except outflow, while allowing easy shaping, considerably enlarge the array of applications of ILs. Thus, they form a promising family of solid electrolyte membranes, which gives access to all-solid devices, a topical industrial challenge in domains such as lithium batteries, fuel cells and dye-sensitized solar cells. Replacing conventional media, organic solvents in lithium batteries or water in proton-exchange-membrane fuel cells (PEMFC), by low-vapour-pressure and non flammable ILs presents major advantages such as improved safety and a higher operating temperature range. Implementation of ILs in separation techniques, where they benefit from huge advantages as well, relies again on the development of supported IL membranes such as ionogels. Moreover, functionalization of ionogels can be achieved both by incorporation of organic functions in the solid matrix, and by encapsulation of molecular species (from metal complexes to enzymes) in the immobilized IL phase, which opens new routes for designing advanced materials, especially (bio)catalytic membranes, sensors and drug release systems (194 references).     

Synthesis and Thermophysical Properties of Ether‐Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf₂]^? anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.     

Liquid phase behavior of ionic liquids with alcohols: experimental studies and modeling

Ionic liquids (ILs) have been suggested as potential "green" solvents to replace volatile organic solvents in reaction and separation processes due to their negligible vapor pressure. To develop ILs for these applications, it is important to gain a fundamental understanding of the factors that control the phase behavior of ionic liquids with other liquids. In this work, we continue our study of the effect of chemical and structural factors on the phase behavior of ionic liquids with alcohols, focusing on pyridinium ILs for comparison to imidazolium ILs from our previous studies. The impact of different alcohol and IL characteristics, including alcohol chain length, cation alkyl chain length, anion, different substituent groups on the pyridinium cation, and type of cation (pyridinium vs imidazolium) will be discussed. In general, the same type of behavior is observed for pyridinium and imidazolium ILs, with all systems studied exhibiting upper critical solution temperature behavior. The impacts of alcohol chain length, cation chain length, and anion, are the same for pyridinium ILs as those observed previously for imidazolium ILs. However, the effect of cation type on the phase behavior is dependent on the strength of the cation-anion interaction. Additionally, all systems from this study and our previous work for imidazolium ILs were modeled using the nonrandom two-liquid (NRTL) equation using two different approaches for determining the adjustable parameters. For all systems, the NRTL equation with binary interaction parameters with a linear temperature dependence provided a good fit of the experimental data.     

CO2/离子液体体系热力学性质的分子动力学模拟

超临界CO2和离子液体(ILs)是两种绿色溶剂. 离子液体可以溶解超临界CO2, 而超临界CO2不能溶解离子液体. 由此设计构成的CO2/IL二元系统, 同时具备了超临界CO2和离子液体的许多优点: 既可以降低离子液体的粘度, 还便于相分离, 是新型的耦合绿色溶剂. 其物理化学性质对于设计反应、分离等过程非常重要. 因此, 本文以CO2/IL二元系统为研究对象, 通过选择合适的分子力场和系综, 运用分子动力学(MD)模拟方法研究了CO2/[bmim][PF6]、CO2/[bmim][NO3]等体系的热力学性质. 结果表明, CO2对ILs膨胀度的影响非常小, 当CO2摩尔分数为0.5时, ILs膨胀仅为15%. CO2/ILs的扩散系数远小于CO2膨胀甲醇、乙醇溶液的扩散系数. 随着CO2含量的增加, ILs的扩散系数提高, 粘度显著下降, 表明CO2能有效地改善ILs扩散性, 减小其粘度. 因此CO2可用以改善离子液体溶剂体系的传递特性, 增强反应分离过程在其中的进行.     

Correlations between phase behaviors and ionic conductivities of (ionic liquid + alcohol) systems

To understand the basic properties of ionic liquids (ILs), we examined the phase behavior and ionic conductivity characteristics using various compositions of different ionic liquids (1-ethyl-3-methylimidazolium hexafluorophosphate [emim] [PF6] and 1-benzyl-3-methylimidazolium hexafluorophosphate [bzmim] [PF6]) in several different alcohols (ethanol, propanol, 1-butanol, 2-butanol, and hexanol). We conducted a systematic study of the impact of different factors on the phase behavior of imidazolium-based ionic liquids in alcohols. Using a new experimental method with a liquid electrolyte system, we observed that the ionic conductivity of the ionic liquid/alcohol was sensitive to the surrounding temperature. We employed Chang et al.’s thermodynamic model [Chang et al. (1997, 1998) [21], [22]] based on the lattice model. The obtained co-ordinated unit parameter from this model was used to describe the phase behavior and ionic conductivities of the given system. Good agreement with experimental data of various alcohol and ILs systems was obtained in the range of interest.     

Ionic liquids in enhancing the sensitivity of capillary electrophoresis: Off‐line and on‐line sample preconcentration techniques

The popularity of ionic liquids (ILs) has grown during the last decade in enhancing the sensitivity of CE through different off‐line or on‐line sample preconcentration techniques. Water‐insoluble ILs were commonly used in IL‐based liquid phase microextraction, in all its variants, as off‐line sample preconcentration techniques combined with CE. Water‐soluble ILs were rarely used in IL‐based aqueous two phase system (IL‐ATPS) as an off‐line sample preconcentration approach combined with CE in spite of IL‐ATPS predicted features such as more compatibility with CE sample injection due to its relatively low viscosity and more compatibility with CE running buffers avoid, in some cases, anion exchange precipitation. Therefore, the attentions for the key parameters affecting the performance of IL‐ATPSs were generally presented and discussed. On‐line CE preconcentration techniques containing IL‐based surfactants at nonmicellar or micellar concentrations have become another interesting area to improve CE sensitivity and it is likely to remain a focus of the field in the endeavor because of their numerous to create rapid, simple and sensitive systems. In this article, significant contributions of ILs in enhancing the sensitivity of CE are described, and a specific overview of the relevant examples of their applications is also given.     

基于离子交换跃迁模型和实验法对离子液体Walden乘积的研究

提出了关于离子液体的新理论——离子交换跃迁模型,通过理论推导得出1：1型离子液体的Walden乘积仅取决于离子对和离子簇直径的统计平均值,即离子液体的阴阳离子结构不同,Walden乘积不同。为了验证模型的正确性,本文合成8种N-烷基-吡啶二氰胺类和N-烷基-咪唑丝氨酸类离子液体,利用上述离子液体的电导率和动力粘度的实验值及文献数据,计算了33种离子液体的Walden乘积。通过比较发现,不同离子液体的Walden乘积不同,即对于离子液体来说,Walden乘积是它的特征物理量。     

Synthesis and characterization of protic ionic liquids containing cyclic amine cations and tetrafluoroborate anion

Several ionic liquids containing pyrrolidinium-, oxopyrrolidinium-, piperidinium-, morpholinium- and trialkylammonium-based cation are synthesized and their thermal property, refractive index, polarity, electrochemical property, and temperature dependency of dynamic viscosity, density and ionic conductivity are characterized. All tetrafluoroborate-based room temperature ionic liquids studied here have a high ionic conductivity (up to 31.4 mS cm^?1). These ILs were successfully used as suitable electrolytes for the diffusion coefficient measurement of ferrocene. Absorbance solvatochromic probes Nile red is used to investigate the relative polarity of these ionic liquids and compared them with several organic solvents. The relation of fluidity to conductance is considered in terms of a Walden plot that is shown to provide a useful basis for organizing the applications of solvent media for ??green?? synthetic reactions.     

Applications of ionic liquids in electrochemical sensors

Ionic liquids (ILs) are molten salts with the melting point close to or below room temperature. They are composed of two asymmetrical ions of opposite charges that only loosely fit together (usually bulky organic cations and smaller anions). The good solvating properties, high conductivity, non-volatility, low toxicity, large electrochemical window (i.e. the electrochemical potential range over which the electrolyte is neither reduced nor oxidized on electrodes) and good electrochemical stability, make ILs suitable for many applications. Recently, novel ion selective sensors, gas sensors and biosensors based on ILs have been developed. IL gels were found to have good biocompatibility with enzymes, proteins and even living cells. Besides a brief discussion of the properties of ILs and their general applications based on these properties, this review focuses on the application of ILs in electroanalytical sensors.     

Poly(dimethylsiloxane)‐Supported Ionogels with a High Ionic Liquid Loading

The immiscibility of poly(dimethylsiloxane) (PDMS) and ionic liquids (ILs) was overcome to create PDMS‐supported IL gels (ionogels) with IL loadings of up to 80 % by mass through a simple sol–gel reaction at room temperature. By stirring a mixture of a functionalized PDMS oligomer, formic acid, and an IL (or lithium‐in‐IL solution), a resin was formed that could be cast to create a freestanding, flexible ionogel. PDMS‐supported ionogels exhibited favorable ionic conductivity (ca. 3 mS cm^?1) and excellent mechanical behavior (elastic modulus: ca. 60 kPa; fatigue life: >5000 cycles; mechanically stable at temperatures up to 200 °C). The activation energy of ionic conductivity was shown to be nearly identical for the ionogel and the neat IL, in contrast to ionogel systems wherein the scaffold material is miscible with the IL. This similarity indicates that IL/scaffold chemical interactions are key to the understanding of ionogel electrical performance, especially at elevated temperatures.     

Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety

Ionic liquids and ionic liquid crystals of imidazolium salts composed of various transition and main group metals have been reviewed. Ionic metal complexes of imidazoles and N-heterocyclic carbenes possess the similar properties were also included. These types of ILs and ILCs have been realized as potential solvents, catalysts, catalyst precursors and reagents for many organic transformations and provide ecofriendly protocols. They have also been found to play key roles in material science. Many of these IL systems are air- and moisture stable and are considered as alternatives for air- and moisture sensitive chloroaluminate-based ILs.     

Effect of water and organic solvents on the ionic dissociation of ionic liquids

The effect of water and several organic solvents on the density, viscosity, and conductivity of ionic liquids (ILs) 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-n-butyl-3-methylimidazolium trifluoroacetate ([bmim][CF3CO2]) was studied at 298.15 K in wide composition ranges. The density, viscosity, and conductivity of the three neat ILs were also determined at various temperatures. Upon the basis of the molar conductivity of the mixtures and that of the neat ILs of the same viscosity, the degree of dissociation of ILs in the solutions was investigated. It can be deduced that the organic solvents enhance the ionic association of the ILs, the effect depending on the solvent dielectric constant, while water promotes dissociation significantly due to its high dielectric constant and its ability to form strong hydrogen bonds with the anions of the ILs.     

Preparation of Room‐Temperature Ionic Liquids by Neutralization of 1,1,3,3‐Tetramethylguanidine with Acids and their Use as Media for Mannich Reaction

Abstract

New room‐temperature ionic liquids (ILs) were prepared by neutralization of 1,1,3,3‐tetramethylguanidine with different acids under ambient condition. The density, viscosity, decomposition temperature, electronic conductivity, and miscibility with some commonly used solvents were determined. As an example of the applications of the new ILs, the reaction of benzaldehyde, aniline, and acetophenone was carried out in the ILs. The ILs are easily prepared in large scale.     

Ionic liquids by proton transfer: vapor pressure, conductivity, and the relevance of DeltapKa from aqueous solutions

We describe the behavior of the conductivity, viscosity, and vapor pressure of various binary liquid systems in which proton transfer occurs between neat Br?nsted acids and bases to form salts with melting points below ambient. Such liquids form an important subgroup of the ionic liquid (IL) class of reaction media and electrolytes on which so much attention is currently being focused. Such "protic ionic liquids" exhibit a wide range of thermal stabilities. We find a simple relation between the limit set by boiling, when the total vapor pressure reaches one atm, and the difference in pK(a) value for the acid and base determined in dilute aqueous solutions. For DeltapK(a) values above 10, the boiling point elevation becomes so high (>300 degrees C) that preemptive decomposition prevents its measurement. The completeness of proton transfer in such cases is suggested by the molten salt-like values of the Walden product, which is used to distinguish good from poor ionic liquids. For the good ionic liquids, the hydrogen bonding of acid molecules to the proton-transfer anion is strong enough that boiling points, but not melting points, may maximize at the hydrogen-bonded dianion composition. High boiling liquids of this type constitute an interesting class of high-temperature protonic acid that may have high-temperature fuel cell applications.