Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than by synthesizing a large array of pure ILs with different chemical structures. In addition, these mixtures can exhibit a range of properties and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control of IL properties for particular applications. However, the fundamental properties, structure, and dynamics of IL mixtures are currently poorly understood, which limits their more widespread application. This article presents the first comprehensive investigation into the bulk and surface properties of IL mixtures formed from two commonly encountered ILs: 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cmim][TfN] and [Cmim][TfN]). Physical property measurements (viscosity, conductivity, and density) reveal that these IL mixtures are not well described by simple mixing laws, implying that their structure and dynamics are strongly composition dependent. Small-angle X-ray and neutron scattering measurements, alongside molecular dynamics (MD) simulations, show that at low mole fractions of [Cmim][TfN], the bulk of the IL is composed of small aggregates of [Cmim] ions in a [Cmim][TfN] matrix, which is driven by nanosegregation of the long alkyl chains and the polar parts of the IL. As the proportion of [Cmim][TfN] in the mixtures increases, the size and number of aggregates increases until the C12 alkyl chains percolate through the system and a bicontinuous network of polar and nonpolar domains is formed. Reactive atom scattering-laser-induced fluorescence experiments, also supported by MD simulations, have been used to probe the surface structure of these mixtures. It is found that the vacuum-IL interface is enriched significantly in C12 alkyl chains, even in mixtures low in the long-chain component. These data show, in contrast to previous suggestions, that the [Cmim] ion is surface active in this binary IL mixture. However, the surface does not become saturated in C12 chains as its proportion in the mixtures increases and remains unsaturated in pure [Cmim][TfN].
The vacuum–liquid interfaces of a number of ionic-liquid mixtures have been investigated using a combination of RAS-LIF, selected surface tension measurements, and molecular dynamics simulations.
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The atomic-level description of liquid interfaces has lagged behind that of solid crystalline surfaces because existing experimental techniques have been limited in their capability to report molecular structure in a fluctuating liquid interfacial layer. We have moved toward a more detailed experimental description of the gas–liquid interface by studying the F-atom scattering dynamics on a common ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. When given contrast by deuterium labeling, the yield and dynamical behavior of reactively scattered HF isotopologues can resolve distinct signatures from the cation butyl, methyl, and ring groups, which help to quantify the relative populations of cation conformations at the liquid–vacuum interface. These results demonstrate the importance of molecular organization in driving site-specific reactions at the extreme outer regions of the gas–liquid interface.
The liquid–vacuum interfaces of a series of ionic liquids (ILs) containing 1-alkyl-1-methylpyrrolidinium ([C n mpyrr]+) cations of different alkyl chain lengths have been studied by reactive-atom scattering with laser-induced fluorescence detection (RAS-LIF) and molecular dynamics (MD) simulations. A direct, quantitative comparison has been performed between [C n mpyrr]+ and the previously better-characterized 1-alkyl-3-methylimidazolium ([C n mim]+) ILs with the same chain lengths, n, and common anion, bis(trifluoromethylsulfonyl)imide ([Tf2N]−). Both RAS-LIF experiments, using O(3P) as the projectile and monitoring OH yield, and MD simulations indicate that the coverage of the surface by alkyl chains is almost independent of the identity of the cation headgroup. Moreover, the potentially abstractable H atoms of the saturated pyrrolidinium ring do not contribute appreciably to the experimental OH yield. In both these senses, therefore, the headgroup is “hidden” from the probe particles approaching from vacuum. More predictably, the alkyl coverage depends strongly and nonstoichiometrically on the length of the alkyl chain, n, for either cation. These results imply the presence of an alkyl-rich layer on the surface formed by preferential orientation of the cations to expose their chains to the vacuum phase. We suggest that the lack of dependence of the packing density of this layer on cation type results from compensating effects of charge density and steric blocking.
The gas–liquid interface of ionic liquids (ILs) is critically important in many applications, for example, in supported IL phase (SILP) catalysis. Methods to investigate the interfacial structure in these systems will allow their performance to be improved in a rational way. In this study, reactive-atom scattering (RAS), surface tension measurements, and molecular dynamics (MD) simulations were used to study the vacuum interface of mixtures of partially fluorinated and normal alkyl ILs. The underlying aim was to understand whether fluorinated IL ions could be used as additives to modify the surface structure of one of the most widely used families of alkyl ILs. The series of ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C n mim][Tf 2 N]) with n = 4–12 were mixed with a fixed-length, semiperfluorinated analogue (1 H ,1 H ,2 H ,2 H -perfluorooctyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 8 mimF 13 ][Tf 2 N]), forming [C n mim] (1– x ) [C 8 mimF 13 ] x [Tf 2 N] mixtures, where x is the bulk mole fraction of the fluorinated component. The RAS-LIF method combined O-atom projectiles with laser-induced fluorescence (LIF) detection of the product OH as a measure of surface exposure of the alkyl chains. For [C 8 mim] (1– x ) [C 8 mimF 13 ] x [Tf 2 N] mixtures, RAS-LIF OH yields are below those expected from stoichiometry. There are quantitatively consistent negative deviations from linearity of the surface tension. Both results imply that the lower-surface-tension fluoroalkyl material dominates the surface. A similar deficit is found for alkyl chain lengths n = 4, 6, 8, and 12 and for all (nonzero) x investigated by RAS-LIF. Accessible-surface-area (ASA) analyses of the MD simulations for [C n mim] (1– x ) [C 8 mimF 13 ] x [Tf 2 N] mixtures qualitatively reproduce the same primary effect of fluoro-chain predominance of the surface over most of the range of n . However, there are significant quantitative discrepancies between MD ASA predictions and experiment relating to the strength of any n -dependence of the relative alkyl coverage at fixed x , and on the x -dependence at fixed ...
The preparation of mixtures of ionic liquids (ILs) represents an attractive strategy to tune their properties and an important aspect is to understand how the structure of the bulk varies...
By mixing ionic liquids (ILs), it is possible to fine-tune their bulk and interfacial structure. This alters their physical properties and solvation behavior and is a simple way to prepare a collection of ILs whose properties can be tuned to optimize a specific application. In this study, mixtures of perfluorinated and alkylated ILs have been prepared, and links between composition, properties, and nanostructure have been investigated. These different classes of ILs vary substantially in the flexibility and polarizability of their chains. Thus, a range of useful structural and physical property variations are accessible through mixing that will expand the library of IL mixtures available in an area that to this point has received relatively little attention. In the experiments presented herein, the physical properties and bulk structure of mixtures of 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide [C 8 MIM][Tf 2 N] and 1-(1H,1H,2H,2H-perfluorooctyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C 8 MIM-F 13 ][Tf 2 N] have been prepared. The bulk liquid structure was investigated using a combination of small-angle X-ray and neutron scattering (SAXS and SANS, respectively) experiments in combination with atomistic molecular dynamics simulations and the measurement of density and viscosity. We observed that the addition of [C 8 MIM-F 13 ][Tf 2 N] to [C 8 MIM][Tf 2 N] causes changes in the nanostructure of the IL mixtures that are dependent on composition so that variation in the characteristic short-range correlations is observed as a function of composition. Thus, while the length scales associated with the apolar regions (polar nonpolar peak�PNPP) increase with the proportion of [C 8 MIM-F 13 ][Tf 2 N] in the mixtures, perhaps surprisingly given the greater volume of the fluorocarbon chains, the length scale of the charge-ordering peak decreases. Interestingly, consideration of the contact peak shows that its origins are both in the direct anion•••cation contact length scale and the nature (and hence volume) of the chains appended to the imidazolium cation.
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