blue ×), formate (HCO 2 − , orange ■ ), hydrogen sulfate (HSO 4 − , yellow-green ▲), and thiocyanate (SCN − , pink +) sourced from unpublished data and ref 28. Note, data points for zero carbon atoms in (B) correspond to the NH 4 [X]salt.
In recent years, a number of different technologies have been proposed for use in reflective displays. One of the most appealing applications of a reflective display is electronic paper, which combines the desirable viewing characteristics of conventional printed paper with the ability to manipulate the displayed information electronically. Electronic paper based on the electrophoretic motion of particles inside small capsules has been demonstrated and commercialized; but the response speed of such a system is rather slow, limited by the velocity of the particles. Recently, we have demonstrated that electrowetting is an attractive technology for the rapid manipulation of liquids on a micrometre scale. Here we show that electrowetting can also be used to form the basis of a reflective display that is significantly faster than electrophoretic displays, so that video content can be displayed. Our display principle utilizes the voltage-controlled movement of a coloured oil film adjacent to a white substrate. The reflectivity and contrast of our system approach those of paper. In addition, we demonstrate a colour concept, which is intrinsically four times brighter than reflective liquid-crystal displays and twice as bright as other emerging technologies. The principle of microfluidic motion at low voltages is applicable in a wide range of electro-optic devices.
Ionic liquids' (ILs) remarkable and tunable physicochemical properties mean they have distinct performance advantages over conventional solvents in many settings. However, the use of ILs in surface-dependent processes (e.g. electrodeposition, heterogeneous catalysis, dye solar cells) is hindered by the lack of a systematic understanding of IL interfacial structure. In this Perspective, we highlight recent experiments which show interfacial IL nanostructure is a consequence of both surface-specific and bulk liquid interactions. These results enable us to develop molecular design rules for controlling interfacial IL behavior.
The bulk structure of the two oldest ionic liquids (ILs), ethylammonium nitrate (EAN) and ethanolammonium nitrate (EtAN), is elucidated using neutron diffraction. The spectra were modelled using empirical potential structure refinement (EPSR). The results demonstrate that EAN exhibits a long-range structure of solvophobic origin, similar to a bicontinuous microemulsion or disordered L(3)-sponge phase, but with a domain size of only 1 nm. The alcohol (-OH) moiety in EtAN interferes with solvophobic association between cation alkyl chains resulting in small clusters of ions, rather than an extended network.
The double layer structure of two ionic liquids (ILs), 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py1,4]FAP) and 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIm]FAP) at the polarized Au(111) electrode interface is probed using Atomic Force Microscopy force measurements. The force-separation profiles suggest a multilayered morphology is present at the electrified Au(111)−IL interface, with more near surface layers detected at higher potentials. At the (slightly negative) open circuit potential, multiple ion layers are present, and the innermost layer, in contact with the Au(111) surface, is enriched in the cation due to electrostatic adsorption. Upon applying negative electrode potentials (−1.0 V, −2.0 V), stronger IL near surface structure is detected: both the number of ion layers and the force required to rupture these layers increases. Positive electrode potentials (+1.0 V, +2.0 V) also enhance IL near surface structure, but not as much as negative potentials, because surface-adsorbed anions are less effective at templating structure in subsequent layers than cations. This interfacial structure is not consistent with a double layer in the Stern−Gouy−Chapman sense, as there is no diffuse layer. The structure is consistent with a capicitative double-layer model, with a very small separation distance between the planes of charge.
The surface interaction of two air- and water-stable ionic liquids (ILs), 1-ethyl-3-methylimidazolium bis[(trifluoromethylsulfonyl]amide ([EMIm]TFSA) and 1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]amide ([BMP]TFSA), with Au(111) has been investigated using atomic force microscopy (AFM), cyclic voltammetry, and scanning tunneling microscopy (STM) measurements. AFM experiments reveal that multiple solvation layers are present at the gold interface for both ILs and that the strength of the interaction between the innermost layer and the substrate is dependent on the cation type; the force required to rupture the innermost solvation layer is greater for [BMP]TFSA than for [EMIm]TFSA, attributed to stronger cation surface interactions. In situ STM elucidates the influence of IL species on restructuring of the Au(111) interface. In the presence of [BMP]TFSA, the Au(111) surface restructures to produce a wormlike pattern, but this unusual morphology is not observed for the [EMIm]TFSA−Au(111) system. This remarkable difference in electrochemical behavior is ascribed to the greater strength of the interaction of [BMP]+ compared to [EMIm]+ with the Au(111) surface. These results demonstrate that such interfacial effects have to be considered for all electrochemical reactions and provide insight into the electrical double-layer structure in IL systems.
The structure and dynamics of the interfacial layers between the extremely pure air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and Au(111) has been investigated using in situ scanning tunneling microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy measurements. The in situ scanning tunnelling microscopy measurements reveal that the Au(111) surface undergoes a reconstruction, and at -1.2 V versus Pt quasi-reference the famous (22 × √3) herringbone superstructure is probed. Atomic force microscopy measurements show that multiple ion pair layers are present at the ionic liquid/Au interface which are dependent on the electrode potential. Upon applying cathodic electrode potentials, stronger ionic liquid near surface structure is detected: both the number of near surface layers and the force required to rupture these layers increases. The electrochemical impedance spectroscopy results reveal that three distinct processes take place at the interface. The fastest process is capacitive in its low-frequency limit and is identified with electrochemical double layer formation. The differential electrochemical double layer capacitance exhibits a local maximum at -0.2 V versus Pt quasi-reference, which is most likely caused by changes in the orientation of cations in the innermost layer. In the potential range between -0.84 V and -1.04 V, a second capacitive process is observed which is slower than electrochemical double layer formation. This process seems to be related to the herringbone reconstruction. In the frequency range below 1 Hz, the onset of an ultraslow faradaic process is found. This process becomes faster when the electrode potential is shifted to more negative potentials.
The lubricating properties of an ionic liquid on gold surfaces can be controlled through application of an electric potential to the sliding contact. A nanotribology approach has been used to study the frictional behavior of 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py(1,4)]FAP) confined between silica colloid probes or sharp silica tips and a Au(111) substrate using atomic force microscopy. Friction forces vary with potential because the composition of a confined ion layer between the two surfaces changes from cation-enriched (at negative potentials) to anion-enriched (at positive potentials). This offers a new approach to tuning frictional forces reversibly at the molecular level without changing the substrates, employing a self-replenishing boundary lubricant of low vapor pressure.
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