INVESTIGATION OF MORPHOLOGICAL AND STRUCTURAL PROPERTIES OF IONIC LIQUID THIN LAYERS ON SOLID SURFACES BY SCANNING PROBE MICROSCOPY
Tesi di Dottorato
Data di Pubblicazione:
2012
Citazione:
INVESTIGATION OF MORPHOLOGICAL AND STRUCTURAL PROPERTIES OF IONIC LIQUID THIN LAYERS ON SOLID SURFACES BY SCANNING PROBE MICROSCOPY / S. Bovio ; coordinatore: M. Bersanelli ; tutore: A. Podesta' ; cotutore: P. Ballone. Universita' degli Studi di Milano, 2012 Jan 24. 24. ciclo, Anno Accademico 2011. [10.13130/bovio-simone_phd2012-01-24].
Abstract:
Molten salts attracted the attention of the scientific community several times during the last century. This interest is motivated by the physico-chemical properties of these systems. In fact, usually molten salts show chemical and thermal stability, i.e. they do not easily decompose or react. Furthermore, these compounds remain liquid over an extended range of temperatures, in which they show also a remarkably low volatility. The fact that molten salts are composed solely by ions, and can have a quite wide electrochemical window, make them very interesting as electrolytes[1].
The main disadvantage in the usage of molten salts in any practical process, is their high melting point (for example as high as 800°C for NaCl), which severely limits the number of reactions that can be done in these media and reduces the possibility of industrial scaling, due to the high energy required to maintain those high temperatures. Since the '70s lower temperature molten salts has been synthesised, like chloroaluminate eutectic mixtures, having melting points around 100°C or even lower, but the real turning point that boosted the research field has been the development of the first water-stable low melting point molten salts, that is what are now usually named room temperature ionic liquids, or simply ionic liquids.
Ionic liquids are usually composed by a big organic cation and a bulky inorganic, water stable, anion: the bulkiness and the complex asymmetric structure of the ions prevent an efficient packaging, leading to a lowering of the coulombic cohesive energy and so of the melting point.
Ionic liquids maintain all the characteristics of the high temperature molten salts, but they are usually liquid at room temperature. This fact induced a renewed interest in the field, as is proved by the several thousand papers published on the topic in 2011.
The community of chemists devoted a great effort to the study of ionic liquids, because of the potential use of those liquids as solvents. Ionic liquids are complex systems, that usually are organised in polar and apolar domains, and can dissolve both polar and apolar species. In addition, there are virtually unlimited choices of ions, and each choice changes the physico-chemical characteristics of the systems: this allows to tailor the properties of the ionic liquids (like miscibility, density, viscosity...), in order to match specific tasks. The characteristics of ionic liquids, last but not least their low vapour pressure, promote them as good solvents for the growing field of the Green Chemistry, in substitution of the volatile organic compounds.
Ionic liquids are also promising as lubricants, in particular in micro- and nano- -electromechanical devices (NEMSs and NEMSs)[2, 3] as well as electrolytes in photoelectrochemical devices used for energy storage and energy production such as supercapacitors[4, 5] or Grätzel solar cells[6]. In all these cases, the most relevant processes determining the performance of the devices, take place at the liquid/solid interface between ILs and solid surfaces: this is a region only a few nanometers thick where the properties of ILs can be significantly different from those of the bulk. The investigation of the interfacial properties of ILs is therefore of primary importance for their technological exploitation. To date, the (bulk)liquid-vapour and solid- (bulk)liquid ILs interfaces have been studied, mostly by sum-frequency generation spectroscopy[7, 8] and by X-ray photoemission spectroscopy[9]. For imidazolium-based ILs, ordering of the ions at the solid/liquid or liquid/ vapour interface has been inferred from vibrational spectroscopy data. For example Mezger et al.[10] performed a study of the (bulk)liquid/solid interface between a negatively charged s
Tipologia IRIS:
Tesi di dottorato
Keywords:
Ionic liquid ; thin film ; AFM ; interface ; layering ; solid surface ; structural properties ; solid-like
Elenco autori:
S. Bovio
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