Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Ionic-liquid materials for the electrochemical challenges of the future.

Ionic liquids (ILs) including ambient-temperature molten salts, which exist in the liquid state even at room temperature, have a long research history. However, their applications were once limited because ILs were considered as highly moisture-sensitive solvents that should be handled in a glove box. After the first synthesis of moisture-stable ILs in 1992, their unique physicochemical properties became known in all scientific fields. ILs are composed solely of ions and exhibit several specific liquid-like properties, e.g., some ILs enable dissolution of insoluble bio-related materials and the use as tailor-made lubricants in industrial applications under extreme physicochemical conditions. Hybridization of ILs and other materials provides quasi-solid materials, which can be used to fabricate highly functional devices. ILs are also used as reaction media for electrochemical and chemical synthesis of nanomaterials. In addition, the negligible vapor pressure of ILs allows the fabrication of electrochemical devices that are operated under ambient conditions, and many liquid-vacuum technologies, such as X-ray photoelectron spectroscopy (XPS) analysis of liquids, electron microscopy of liquids, and sputtering and physical vapor deposition onto liquids. In this article, we review recent studies on ILs that are employed as functional advanced materials, advanced mediums for materials production, and components for preparing highly functional materials.

New frontiers in materials science opened by ionic liquids.

Polyaniline nanostructures and the role of aniline oligomers in their formation

Ionic liquids (ILs), in particular imidazolium-based ILs, have proven to be suitable media for the generation and stabilisation of soluble metal nanoparticles (NPs). Indeed, transition-metal NPs with small sizes, narrow size distribution and different shapes have been prepared by reduction of organometallic compounds with molecular hydrogen, decomposition of transition-metal complexes in the zero-valent state, metal bombardment or simple transfer for previously prepared water- or classical organic solvent-soluble colloids to the ILs. The formation and stabilisation of NPs in these highly hydrogen bonded organised supramolecular fluids occur with the re-organisation of the hydrogen bond network and the generation of nanostructures with polar and non-polar regions, including the NPs. The IL forms a protective layer, which is probably composed of imidazolium aggregates located immediately adjacent to the nanoparticle surface, which provides both steric and electronic protection against aggregation and/or agglomeration. These stable transition-metal NPs immobilised in the ILs have proven to be efficient green catalysts for several reactions in multiphase conditions and also novel materials for chemical sensors. In this critical review, the structural/surface properties of these soluble metal NPs dispersed in ILs and their application in catalysis and as chemical sensors are discussed, with particular attention paid to the stabilisation models proposed to explain the stability and properties of these metal NPs (219 references).

On the structural and surface properties of transition-metal nanoparticles in ionic liquids

Polyaniline (PANI) is prepared by the oxidation of aniline. Depending on the acidity conditions during the chemical oxidation, different types of products can be identified. The aniline dimers, semidines, are the first oxidation products. In the next step, aniline trimers containing a phenazine moiety, the nucleates, are produced. At moderate acidity, pH > 3.5, the reaction pathway further leads to higher brown non-conducting aniline oligomers. Alternatively, when the acidity is sufficiently high, pH  The model of phenazine nucleates is offered to explain the various supramolecular nanostructures produced by PANI. It is proposed that the hydrophobic nucleates randomly aggregate in the aqueous phase or become organized to form one-dimensional stacks stabilized by π–π interactions. This step is followed by the growth of PANI chains from the self-assembled nucleates. The evolution of the nanostructures is conveniently observed by the combination of microscopic and spectroscopic techniques. The random agglomeration of nucleates gives rise to PANI granules and regular self-assembly into stacks subsequently leads to PANI nanofibers. The growth of other nanostructures requires a starting template. A model of a flowing template combined with a helical nanotubular growth is proposed to account for the formation of nanotubes, monomer droplets serve as templates for microspheres. The detailed chemical structure of nucleates has still to be elucidated. The nucleates adsorb and self-assemble along various interfaces giving subsequently rise to additional conducting polymer morphologies. The adsorption of nucleates at solid surfaces immersed in the reaction mixture leads to PANI nanofilms or coatings of various substrates. The competition between nucleate adsorption and nucleate self-assembly may lead to more complex morphologies combining one-dimensional and three-dimensional features, such as nanobrushes, hairy spheres, etc . The control of nucleates self-assembly and of PANI growth, the involvement of various interfaces in this process, and the role of PANI conductivity are discussed. The nanostructures produced by other conducting polymers, especially by substituted PANI, polypyrrole, or poly(3,4-ethylenedioxythiophene) are also considered. Two potential extensions to the preparation of related materials, such as nitrogen-containing carbonized PANI nanostructures or the composites of conducting polymers with noble metals are outlined. The present review accounts for the latest development in the realm of PANI nanostructures in past few years and provides an upgrade in the models proposed for their formation.

Polyaniline Nanostructures and the Role of Aniline Oligomers in Their Formation

Development of new techniques for scanning electron microscope observation using ionic liquid

We report that ionic liquids (ILs) can be observed by electron microscopy without any charging of the liquid. Based on this, we present an in situ electrochemical scanning electron microscopy (in situ ECSEM) system. The key technology that enables in situ ECSEM is that charges can be removed from an IL by grounding it with a Pt wire, even if the IL is in an insulating glass cell. As a first demonstration, we describe the redox reaction of a polypyrrole (PPy) film accompanied by changes in its thickness when it is polarized by the film-deposited Pt electrode in the IL. Furthermore, energy-dispersive X-ray fluorescence (EDX) analysis can be employed for the electrode polarized in the IL. The component analysis by EDX of PPy in an IL containing K+ as a marker, reveals doping of electrolyte cations into the PPy film upon the latter's reduction and dedoping of cations from the film upon oxidation.

Development of in situ electrochemical scanning electron microscopy with ionic liquids as electrolytes.

Development of in situ scanning electron microscope system for real time observation of metal deposition from ionic liquid

The electrodeposition of Al-Mo-Ti ternary alloys was examined in the Lewis acidic 66.7-33.3% mole fraction aluminum chloride-l-ethyl-3-methylimidazolium chloride (AlCl 3 -EtMelmCl) room-temperature ionic liquid containing (Mo 6 Cl 8 )Cl 4 and TiCl 2 . The Mo content in the alloys varied with the applied current density and the Mo(II)/Ti(II) concentration ratio. The Ti content was small and constant at 0.6 ± 0.2% atomic fraction (a/o) and was independent of the deposition conditions. All the electrodeposited Al-Mo-Ti alloys were dense and compact and adhered well to the copper substrate. The deposit surface morphology depended on the applied current density and the Mo content of the alloys, as reported previously for the amorphous binary Al-Mo alloys. However, no amorphous glass phase could be detected in the Al-Mo-Ti ternary alloy samples; this behavior may be related to the presence of Ti. In summary, the addition of a small amount of Ti (∼ 1 a/o) to the binary Al-Mo alloys resulted in a ternary alloy with a substantially improved chloride-induced pitting corrosion resistance compared to the related Al-Mo alloy.

Electrodeposition of Al–Mo–Ti Ternary Alloys in the Lewis Acidic Aluminum Chloride–1-Ethyl-3-methylimidazolium Chloride Room-Temperature Ionic Liquid

Anodic Oxidation of Hydrogenated Amorphous Silicon and Properties of Oxide

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