Professor Rob Atkin

© 2016 The Royal Society of Chemistry.Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ~60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al3+ system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made.

© the Owner Societies 2016.Atomic force microscopy has been used to study the effect of temperature on normal forces and friction for the room temperature ionic liquid (IL) ethylammonium nitrate (EAN), confined between mica and a silica colloid probe at 25 °C, 50 °C, and 80 °C. Force curves revealed a strong fluid dynamic influence at room temperature, which was greatly reduced at elevated temperatures due to the reduced liquid viscosity. A fluid dynamic analysis reveals that bulk viscosity is manifested at large separation but that EAN displays a nonzero slip, indicating a region of different viscosity near the surface. At high temperatures, the reduction in fluid dynamic force reveals step-like force curves, similar to those found at room temperature using much lower scan rates. The ionic liquid boundary layer remains adsorbed to the solid surface even at high temperature, which provides a mechanism for lubrication when fluid dynamic lubrication is strongly reduced. The friction data reveals a decrease in absolute friction force with increasing temperature, which is associated with increased thermal motion and reduced viscosity of the near surface layers but, consistent with the normal force data, boundary layer lubrication was unaffected. The implications for ILs as lubricants are discussed in terms of the behaviour of this well characterised system.

© 2016 American Chemical Society.Atomic force microscopy (AFM), density functional theory (DFT) calculations, and contact angle measurements have been used to investigate the liquid-highly ordered pyrolytic graphite (HOPG) electrode interface for three deep eutectic solvents (DESs) as a function of applied potential. The DESs examined are 1:2 mixtures of choline chloride and urea (ChCl:urea), choline chloride and ethylene glycol (ChCl:ethylene glycol), and choline chloride and glycerol (ChCl:glycerol). DFT calculations reveal that in all cases the molecular component is excluded from the graphite interface at all potentials, while chloride and choline are attracted into the Stern layer at positive and negative potentials, respectively. AFM force curves confirm these trends and also show that the first near surface liquid layer in contact with the Stern layer is rich in the molecular component. The extent of near surface layering increases with potential and the hydrogen bonding capacity of the molecular component. The variation in the macroscopic contact angle with potential is consistent with changes in the Stern layer composition.

© 2015 Elsevier Ltd. All rights reserved.The electrochemical reduction of 0.1 M TaF5 in two hydrophobic ionic liquids (1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4]FAP) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) amide ([Py1,4]TFSA) is probed using three in situ techniques: scanning tunneling microscopy (STM), atomic force microscopy (AFM), and electrochemical quartz crystal microbalance (EQCM). These techniques reveal that under similar conditions TaF5 is more easily reduced in the liquids with [TFSA]- than [FAP]-anions. Increasing the temperature reduced the viscosity and density of the ionic liquids which facilitates TaF5 electroreduction, in particular, in [Py1,4]TFSA. A herringbone reconstruction of the Au electrode was observed by STM for both ionic liquids with and without TaF5. Ta deposition was proved by STM and EQCM in [Py1,4]TFSA. Cracked layers, with ionic liquid trapped inside, were obtained by direct plating from the [TFSA]- ionic liquid. No Ta containing deposits could be obtained in the liquid with the [FAP]- anion.

© The Royal Society of Chemistry 2016.Solvent penetration experiments and small-angle X-ray scattering reveal that phospholipids dissolved in a deep eutectic solvent (DES) spontaneously self-assemble into vesicles above the lipid chain melting temperature. This means DESs are one of the few nonaqueous solvents that mediate amphiphile self-assembly, joining a select set of H-bonding molecular solvents and ionic liquids.

© 2015 American Chemical Society.Small angle neutron scattering has been used to probe the self-assembled structures formed by novel block copolymers in water and two protic ionic liquids (ILs), ethylammonium nitrate (EAN) and propylammonium nitrate (PAN). The block copolymers consist of solvophilic poly(ethylene oxide) (PEO) tethered to either poly(ethyl glycidyl ether) (PEGE) or poly(glycidyl propyl ether) (PGPrE) solvophobic blocks. Four block copolymers (EGE109EO54, EGE113EO115, EGE104EO178, and GPrE98EO260) have been investigated between 10 and 100 °C, showing how aggregate structure changes with increasing the EO block length, by changing the insoluble block from EGE to the more bulky, hydrophobic GPrE block, and with temperature. EO solubility mainly depends on the hydrogen bond network density, and decreases in the order H2O, EAN, and then PAN. The solubility of the EGE and GPrE blocks decreases in the order PAN, EAN then water because the large apolar domain of PAN increase the solubility of the solvophobic blocks more effectively than the smaller apolar domains in EAN, and water, which is entirely hydrophilic; GPrE is less soluble than EGE because its larger size hinders solubilization in the IL apolar domains. Large disk-shaped structures were present for EGE109EO54 in all three solvents because short EO chains favor flat structures, while GPrE98EO260 formed spherical structures because long EO chains lead to curved aggregates. The aggregate structures of EGE113EO115 and EGE104EO178, which have intermediate EO chain lengths, varied depending on the solvent and the temperature. Solubilities also explain trends in critical micelle concentrations (cmc) and temperatures (cmt).

Copyright © 2014 Published by Elsevier Ltd. All rights reserved.Three Australian sub-bituminous coals were treated with three different ionic liquids (ILs) at a temperature of 100 °C. The thermal behaviour of these treated coals were compared against raw coals via pyrolysis experiments in a Thermogravimetric Analyser. Morphological comparisons were also made via Scanning Electron Microscopy. Among the studied ILs, 1-butyl-3-methylimidazolium chloride [Bmim][Cl] was found to perform the most consistently in being able to alter the thermal and morphological properties of most of the coals used. It is posited that this may be due to the large difference in charge density between the delocalised charge of the large bmim cation and the chloride anion which allows this IL to disrupt the cross linked network of coal. It was also found that the interactions of the ionic liquids are coal specific, for instance none of the ionic liquids were able to change the thermal properties of coal A. Moreover, the results indicated that among the studied coals, coal R showed the highest mass loss during pyrolysis in TGA and coal C showed the highest amount of swelling and fragmentation in SEM images. The results displayed in this study indicate that the potential for ionic liquids to be used as pre-treatments in coal liquefaction is promising. Crown

This journal is © the Owner Societies.In situ amplitude modulated-atomic force microscopy (AM-AFM) has been used to probe the nanostructure of mixtures of propylammonium nitrate (PAN) with n-alkanols near a mica surface. PAN is a protic ionic liquid (IL) which has a bicontinuous sponge-like nanostructure of polar and apolar domains in the bulk, which becomes flatter near a solid surface. Mixtures of PAN with 1-butanol, 1-octanol, and 1-dodecanol at 10-70 vol% n-alkanol have been examined, along with each pure n-alkanol, to reveal the effect of composition and n-alkanol chain length. At low concentrations the butanol simply swells the PAN near-surface nanostructure, but at higher concentrations the nanostructure fragments. Octanol and dodecanol first lower the preferred curvature of the PAN near-surface nanostructure because, unlike n-butanol, their alkyl chains are too long to be accommodated alongside the PAN cations. At higher concentrations, octanol and dodecanol self-assemble into n-alkanol rich aggregates in a PAN rich matrix. The concentration at which aggregation first becomes apparent decreases with n-alkanol chain length.

This journal is © the Owner Societies.Colloid probe friction force microscopy (FFM) has been used to study the lubricity of propylammonium nitrate (PAN) mixed with n-alkanols confined between sliding silica and mica surfaces. Mixtures of PAN with butanol, hexanol, octanol and dodecanol were investigated for various n-alkanol volume fractions to elucidate the effect of n-alkanol hydrocarbon chain length and concentration on shear forces. For all n-alkanols friction decreases with n-alkanol vol%. The trends in friction reduction with n-alkanol vol% do not correlate with changes in the bulk phase viscosity or the near surface nanostructure, and colloid probe atomic force microscope (AFM) fluid dynamic measurements showed that none of the mixtures shear thin. Thus, the reduction in friction is attributed to the n-alkanol disrupting solvophobic interactions between boundary layer propylammonium ions adsorbed to the mica and near surface liquid layers. The lowest friction is obtained for pure dodecanol, which is attributed to the dodecanol forming a robust boundary layer. Friction for the other pure n-alkanols is higher because the lateral attractions between adsorbed n-alkanols are too weak to facilitate the formation of a strong boundary layer, commensurate with the decreased hydrocarbon chain length.

© 2015 American Chemical Society.Ionic liquids (ILs) are attractive solvents for devices such as lithium ion batteries and capacitors, but their uptake is limited, partially because their Stern layer nanostructure is poorly understood compared to molecular solvents. Here, in situ amplitude-modulated atomic force microscopy has been used to reveal the Stern layer nanostructure of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm TFSI)-HOPG (highly ordered pyrolytic graphite) interface with molecular resolution. The effect of applied surface potential and added 0.1 wt/wt % Li TFSI or EMIm Cl on ion arrangements is probed between ±1 V. For pure EMIm TFSI at open-circuit potential, well-defined rows are present on the surface formed by an anion-cation-cation-anion (A-C-C-A) unit cell adsorbed with like ions adjacent. As the surface potential is changed, the relative concentrations of cations and anions in the Stern layer respond, and markedly different lateral ion arrangements ensue. The changes in Stern layer structure at positive and negative potentials are not symmetrical due to the different surface affinities and packing constraints of cations and anions. For potentials outside ±0.4 V, images are featureless because the compositional variation within the layer is too small for the AFM tip to detect. This suggests that the Stern layer is highly enriched in either cations or anions (depending on the potential) oriented upright to the surface plane. When Li⁺ or Cl^- is present, some Stern layer ionic liquid cations or anions (respectively) are displaced, producing starkly different structures. The Stern layer structures elucidated here significantly enhance our understanding of the ionic liquid electrical double layer.

© The Royal Society of Chemistry 2015.Electrochemical quartz crystal microbalance has been used to measure changes in the composition of the capacitive electrical double layer for 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate, an ionic liquid, in contact with a gold electrode surface as a function of potential. The mass difference between the cation and anion means that the technique can effectively "weigh" the surface charge accurately with high temporal resolution. This reveals quantitatively how changing the potential alters the ratio of cations and anions associated with the electrode surface, and thus the charge per unit area, as well as the kinetics associated with these interfacial processes. The measurements reveal that it is diffusion of co-ions into the interfacial region rather than expulsion of counterions that controls the relaxation. The measured potential dependent double layer capacitance experimentally validates recent theoretical predictions for counterion overscreening (low potentials) and crowding (high potentials) at electrode surfaces. This new capacity to quantitatively measure ion composition is critical for ionic liquid applications ranging from batteries, capacitors and electrodeposition through to boundary layer structure in tribology, and more broadly provides new insight into interfacial processes in concentrated electrolyte solutions.

© 2015 American Chemical Society.Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (~165°).

© 2015 American Chemical Society.Two Australian thermal coals were treated with four different ionic liquids (ILs) at temperatures as low as 100 °C. The ILs used were 1-butylpyridinium chloride ([Bpyd][Cl]), 1-ethyl-3-methylimidazolium dicyanamide ([Emim][DCM]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), and 1-butyl-3-methylimidazolium tricyanomethanide ([Bmim][TCM]). Visual comparisons were made between the raw and IL-treated coals via optical microscopy. Changes in thermal behavior of these treated coals were compared against raw coals via pyrolysis experiments in a thermogravimetric analyzer (TGA). Changes in functional group composition in the treated coals were probed via Fourier transform infrared (FTIR) spectroscopy. The recovered ILs were also analyzed via FTIR and nuclear magnetic resonance (NMR) spectroscopies to observe any changes after recovery. Low-temperature IL treatment of each of the coals resulted in fragmentation and fracturing, reducing the average particle size. An increase in mass loss in the treated coals was also observed when compared to each raw coal, indicating an increase in lower molecular weight fragments after treatment. This was corroborated by a large increase in aliphatic hydrocarbons being observed in the treated coals, along with a decrease in oxygenated functional groups and mineral matter in one coal. The recovered ILs were shown to be unchanged by this treatment process, indicating their potential recyclability. These results indicate the potential for ILs to be implemented as solvent treatments for coal conversion processes.

© 2015.Research into the properties and applications of ionic liquids (ILs) has accelerated over the last few decades, driven principally by the advanced reaction kinetics and specificity they offered for synthesis and catalysis. ILs display many highly desirable properties, including high electrical and thermal conductivities and wide electrochemical windows, all of which can be tuned by altering the nature of their constituent ions. The discovery that ILs mediate surfactant self-assembly increased interest further. X-ray and neutron scattering are powerful tools for elucidating structure in both simple and complex, mesostructured liquids that were soon applied to IL-based systems. Early work revealed that many IL solvents are themselves nanostructured, and comprise distinct polar and apolar domains produced by the solvophobic segregation of alkyl moieties. Over the last decade scattering techniques have been used to characterise the nanostructure of a diverse range of ILs. Recently, nanostructure changes in ILs produced by the dissolution of salts, polymers, small molecules and amphiphiles have begun to be elucidated. X-ray and neutron scattering have, and will continue to, play a fundamental role in understanding structure-property relationships in IL-based systems.

© 2016 Elsevier B.V.Two lignite samples (150-212. µm) were treated with four ionic liquids (ILs); 1-butylpyridinium chloride ([Bpyd][Cl]), 1-ethyl-3-methylimidazolium dicyanamide ([Emim][DCA]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) and 1-butyl-3-methylimidazolium tricyanomethanide ([Bmim][TCM]) at 100. °C for 3. h to establish the utility of ILs for lignite pre-treatment in conversion processes. ILs are room temperature molten salts that have remarkable physical and chemical properties including high thermal and electrochemical stabilities, low vapour pressures and, critically for this work, the capacity to solubilise a diverse range of materials. Thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and optical microscopy were employed in this study to gain insight into the physical and chemical interactions occurring between lignite and ILs at low temperatures. The FTIR results indicate that the majority of the ILs employed were able to break apart the macro-structure of coal resulting in an increase in short chain aliphatic hydrocarbons. Additionally, FTIR analysis revealed a significant decrease in the presence of COOH and CO groups for lignites treated with [Emim][DCM]. The TGA data revealed that the IL treated lignites had significantly lower devolatilisation temperatures than the untreated lignite, indicating an increase in lower molecular weight species after treatment. Microscopy showed a sizeable decrease in particle size after IL treatment due to fragmentation, and these coals appeared to be considerably swollen. Analysis of the recovered ILs showed no denaturing after the treatment process, indicating their recyclability potential in the treatment process.

© the Owner Societies 2015.The structure and interactions of different (Li salt + glyme) mixtures, namely equimolar mixtures of lithium bis(trifluoromethylsulfonyl)imide, nitrate or trifluoroacetate salts combined with either triglyme or tetraglyme molecules, are probed using Molecular Dynamics simulations. structure factor functions, calculated from the MD trajectories, confirmed the presence of different amounts of lithium-glyme solvates in the aforementioned systems. The MD results are corroborated by S(q) functions derived from diffraction and scattering data (HEXRD and SAXS/WAXS). The competition between the glyme molecules and the salt anions for the coordination to the lithium cations is quantified by comprehensive aggregate analyses. Lithium-glyme solvates are dominant in the lithium bis(trifluoromethylsulfonyl)imide systems and much less so in systems based on the other two salts. The aggregation studies also emphasize the existence of complex coordination patterns between the different species (cations, anions, glyme molecules) present in the studied fluid media. The analysis of such complex behavior is extended to the conformational landscape of the anions and glyme molecules and to the dynamics (solvate diffusion) of the bis(trifluoromethylsulfonyl)imide plus triglyme system.

© 2015 The Royal Society of Chemistry.The nature of amphiphilic self-assembly in alkylammonium protic ionic liquids (PILs) is examined by systematically varying the ionic structure and composition, H-bonding capacity, and nanostructure of both the PIL and micelle-forming cationic surfactant, and contrasted with self-assembly in water. Using small-angle neutron scattering, micelle structure and concentrations are determined for primary-quaternary dodecylammonium salts in nitrate and thiocyanate PILs. While the solvophobic driving force depends only on the average polarity of the PIL, surprisingly strong, specific interactions of the head group and counterion with the PIL H-bond network are found. This suggests the importance of developing designer amphiphiles for assembling soft matter structures in PILs.

The interactions between vitrinite and inertinite-rich coals and the ionic liquid butylimidazolium chloride ([bmim][Cl]) heated to 100 C have been characterised. Differences in the interactions of coal macerals and ionic liquids have been identified. [bmim][Cl] is able to dissolve 22 wt% of a high-vitrinite coal fraction compared to 14 wt% of a high-inertinite coal fraction. The vitrinite-rich coal fraction tends to swell to a greater extent compared to the inertinite-rich coal fraction, which was fractured and fragmented rather than swelled. © 2013 Published by Elsevier Ltd. All rights reserved.

Steady shear viscosity measurements have been performed on 100. kDa poly(ethylene oxide) (PEO) dissolved in the protic ionic liquids ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) and in water. The zero shear viscosity in all three solvents increases with polymer concentration, falling into three concentration regimes corresponding to dilute, semi-dilute and network solutions. Huggins plots reveal three distinct solvent conditions: good (water), good-theta (EAN) and theta (PAN). However, differences in the transition concentrations, power law behaviour of the viscosities, and relaxation times arising from shear thinning in the two ILs can be directly related to the effects of solvent nanostructure. © 2014 Elsevier Inc.

Atomic force microscopy (AFM) force measurements elucidate the effect of cation alkyl chain length and the anion species on ionic liquid (IL) interfacial structure at highly ordered pyrolytic graphite (HOPG) surfaces as a function of potential. Three ILs are examined: 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM] FAP), 1-ethyl-3- methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM] FAP), and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] TFSA). The step-wise force-distance profiles indicate the ILs adopt a multilayered morphology near the surface. When the surface is biased positively or negatively versus Pt quasireference electrode, both the number of steps, and the force required to rupture each step increase, indicating stronger interfacial structure. At all potentials, push-through forces for [HMIM] FAP are the highest, because the long alkyl chain results in strong cohesive interactions between cations, leading to well-formed layers that resist the AFM tip. The most layers are observed for [EMIM] FAP, because the C2 chains are relatively rigid and the dimensions of the cation and anion are similar, facilitating neat packing. [EMIM] TFSA has the smallest push-through forces and fewest layers, and thus the weakest interfacial structure. Surface-tip attractive forces are measured for all ILs. At the same potential, the attractions are the strongest for [EMIM] TFSA and the weakest for [HMIM] FAP because the interfacial layers are better formed for the longer alkyl chain cation. This means interfacial forces are stronger, which masks the weak attractive forces. © 2014 IOP Publishing Ltd.

Ionic liquids (IL) exhibit a remarkably diverse interfacial chemistry, with multiple interfacial layers present at the IL/solid interface. Ionic liquids (ILs) are pure salts with melting points typically less than 100°C. It has remarkable physical properties, which include wide electrochemical stability windows, high ionic conductivity and negligible vapor pressure. The adsorption strength of ILs onto solid surfaces is much higher than for typical organic solvents or water. The structure and composition of the interfacial layer can be tuned by varying the surface potential and the ionic structure, and by addition of solutes. This allows us to envision that IL interfacial properties can be readily matched to a particular application once the required fundamental understanding is elucidated. STM and AFM results show that the IL cation has a strong influence on the structure and composition of the interface.

The nanostructure of a 50:50 vol% mixture of glycerol and ethylammonium formate (EAF), a protic ionic liquid (IL), has been investigated using neutron diffraction and empirical potential structure refinement (EPSR) fits. EPSR fits reveal that the mixture is nanostructured. Electrostatic interactions between IL charge groups leads to the formation of ionic regions. These solvophobically repel cation alkyl groups which cluster together to form apolar domains. The polar glycerol molecules are preferentially incorporated into the charged domains, and form hydrogen bonds with EAF groups rather than with other glycerol molecules. However, radial distribution functions reveal that glycerol molecules pack around each other in a fashion similar to that found in pure glycerol. This suggests that a glycerol channel runs through the ionic domain of EAF. The absence of significant glycerol-glycerol hydrogen bonding indicates that glycerol molecules are able to span the polar domain, bridging EAF charge groups. Glycerol can adopt six distinct conformations. The distribution of conformers in the EAF mixture is very different to that found in the pure liquid because hydrogen bonds form with EAF rather than with other glycerol molecules, which imparts different packing constraints. © 2014 The Owner Societies.

© 2014 American Chemical Society.The thermal conductivities of nine protic ionic liquids (ILs) have been investigated between 293 and 340 K. Within this range, the thermal conductivities are between 0.18 and 0.30 W·m-1·K-1. These values are higher than those typically associated with oils and aprotic ILs, but lower than those of strongly hydrogen bonding solvents like water. Weak linear decreases in thermal conductivity with temperature are noted, with the exception of ethanolammonium nitrate (EtAN) where the thermal conductivity increases with temperature. The dependence of thermal conductivity on IL type is analyzed with use of the Bahe-Varela pseudolattice theory. This theory treats the bulk IL as an array of ordered domains with intervening domains of uncorrelated structure which enable and provide barriers to heat propagation (respectively) via allowed vibrational modes. For the protic ILs investigated, thermal conductivity depends strongly on the IL cation alkyl chain length. This is because the cation alkyl chain controls the dimensions of the IL bulk nanostructure, which consists of charged (ordered domains) and uncharged regions (disordered domains). As the cation alkyl chain controls the dimensions of the disordered domains, it thus limits the thermal conductivity. To test the generality of this interpretation, the thermal conductivities of propylammonium nitrate (PAN) and PAN-octanol mixtures were examined; water selectively swells the PAN charged domain, while octanol swells the uncharged regions. Up to a certain concentration, adding water increases thermal conduction and octanol decreases it, as expected. However, at high solute concentrations the IL nanostructure is broken. When additional solvent is added above this concentration the rate of change in thermal conductivity is greatly reduced. This is because, in the absence of nanostructure, the added solvent only serves to dilute the salt solution.

© 2014 American Chemical Society.Density functional tight binding (DFTB), which is ~100-1000 times faster than full density functional theory (DFT), has been used to simulate the structure and properties of protic ionic liquid (IL) ions, clusters of ions and the bulk liquid. Proton affinities for a wide range of IL cations and anions determined using DFTB generally reproduce G3B3 values to within 5-10 kcal/mol. The structures and thermodynamic stabilities of n-alkyl ammonium nitrate clusters (up to 450 quantum chemical atoms) predicted with DFTB are in excellent agreement with those determined using DFT. The IL bulk structure simulated using DFTB with periodic boundary conditions is in excellent agreement with published neutron diffraction data.

The highly ordered pyrolytic graphite (HOPG)/1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIm]Tf2N) interface is examined by ultrahigh vacuum scanning tunneling microscopy (UHV-STM), atomic force microscopy (UHV-AFM) (and as a function of potential by in situ scanning tunneling microscopy (STM)), in situ atomic force microscopy (AFM), and density functional theory (DFT) calculations. In situ STM and AFM results reveal that multiple ionic liquid (IL) layers are present at the HOPG/electrode interface at all potentials. At open-circuit potential (OCP), attractions between the cation alkyl chain and the HOPG surface result in the ion layer bound to the surface being cation rich. As the potential is varied, the relative concentrations of cations and anions in the surface layer change: as the potential is made more positive, anions are preferentially adsorbed at the surface, while at negative potentials the surface layer is cation rich. At -2 V an unusual overstructure forms. STM images and AFM friction force microscopy measurements both confirm that the roughness of this overstructure increases with time. DFT calculations reveal that [OMIm]+ is attracted to the graphite surface at OCP; however, adsorption is enhanced at negative potentials due to favorable electrostatic interactions, and at -2 V the surface layer is cation rich and strongly bound. The energetically most favorable orientation within this layer is with the [OMIm]+ octyl chains aligned "epitaxially" along the graphitic lattice. This induces quasi-crystallization of cations on the graphite surface and formation of the overstructure. An alternative explanation may be that, because of the bulkiness of the cation sitting along the surface, a single layer of cations is unable to quench the surface potential, so a second layer forms. The most energetically favorable way to do this might be in a quasi-crystalline/multilayered fashion. It could also be a combination of strong surface binding/orientations and the need for multilayers to quench the charge. © 2014 American Chemical Society.

In this overview paper we present a combined in situ STM, AFM and EIS study on the structure and dynamics of the interfacial layers between Au(111) and two extremely pure ionic liquids, namely [Py1,4]FAP and [EMIM]FAP. The combination of these methods provides valuable information for both neutral and electrified interfaces. In situ STM and AFM results reveal that a multilayered ion morphology is present at the IL-Au(111) interface, with stronger near surface layering detected at higher electrode potentials. The in situ STM measurements show that the structure of the interfacial layers is dependent on the applied electrode potential, the number of subsequent STM scans and the scan rate. Furthermore, in the case of [Py1,4]FAP, the Au(111) surface undergoes herringbone reconstruction, Au(111)(22×3), in the cathodic potential regime, and the ultra-slow formation of vacancies in the herringbone structure is probed with in situ STM. EIS measurements reveal the presence of two distinct capacitive processes at the interface taking place on different time scales. The time scale of the fast process is typically in the millisecond range and is governed by the bulk ion transport in the IL, which exhibits a Vogel-Fulcher-Tammann-type temperature dependence. The slow process takes place on a time scale of seconds and is Arrhenius activated. The contribution of this process to the overall interfacial capacitance is particularly large in the potential regime where the herringbone structure is probed. Furthermore, we analyze the temperature dependence of the interfacial capacitance. © 2013 Elsevier B.V. All rights reserved.

Silica particle suspensions of 10 wt % have been investigated in the protic ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), propylammonium nitrate (PAN), and dimethylethylammonium formate (DMEAF). Static and dynamic light scattering reveal that single particles coexist in dynamic equilibrium with flocculated networks at room temperature. These types of systems are classified as weakly flocculated and are quite rare. As weakly flocculated systems generally exist only within a narrow range of conditions, the effect of temperature was probed. When temperature is increased, the thermal motion of suspended particles increases, favoring dispersion, but in ILs suspensions, heating reduces the stabilizing effect of the interfacial structure of the IL. When subjected to a small increase in temperature, particle suspensions in ILs become unstable, indicated by the absence of a peak corresponding to single particles in the light scattering data. For EAN and DMEAF, further increasing temperatures above 40 C returns the systems to a weakly flocculated state in which thermal energy is sufficient to break particles away from aggregates. Weakly flocculated suspensions in EAN and EtAN settle more rapidly than predicted by the Stokes equation, as the particles spend a significant portion of time in large, rapidly settling flocs. Surprisingly, suspensions in PAN and DMEAF settle slower than predicted. Oscillatory rheology indicates that these suspensions are viscoelastic, due to a persistent, long-range structure in the suspension that slows settling. In aggregated systems, settling is very rapid. © 2014 American Chemical Society.

The partitioning constants and Gibbs free energies of transfer of poly(oxyethylene) n-alkyl ethers between dodecane and the protic ionic liquids (ILs) ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) are determined. EAN and PAN have a sponge-like nanostructure that consists of interpenetrating charged and apolar domains. This study reveals that the ILs solvate the hydrophobic and hydrophilic parts of the amphiphiles differently. The ethoxy groups are dissolved in the polar region of both ILs by means of hydrogen bonds. The environment is remarkably water-like and, as in water, the solubility of the ethoxy groups in EAN decreases on warming, which underscores the critical role of the IL hydrogen-bond network for solubility. In contrast, amphiphile alkyl chains are not preferentially solvated by the charged or uncharged regions of the ILs. Rather, they experience an average IL composition and, as a result, partitioning from dodecane into the IL increases as the cation alkyl chain is lengthened from ethyl to propyl, because the IL apolar volume fraction increases. Together, these results show that surfactant dissolution in ILs is related to structural compatibility between the head or tail group and the IL nanostructure. Thus, these partitioning studies reveal parameters for the effective molecular design of surfactants in ILs. Surfactants in ionic liquids: The dissolution and solvation of the hydrophilic and hydrophobic components of non-ionic surfactants in ionic liquids are affected by solvent nanostructure and hydrogen bonding. The polar domains of protic ionic liquids ethyl- and propylammonium nitrate are, thermodynamically speaking, remarkably water-like. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.