2 resultados para DOUBLE-QUANTUM-DOT
em AMS Tesi di Dottorato - Alm@DL - Università di Bologna
Resumo:
Traditional logic gates are rapidly reaching the limits of miniaturization. Overheating of these components is no longer negligible. A new physical approach to the machine was proposed by Prof. C S. Lent “Molecular Quantum cellular automata”. Indeed the quantum-dot cellular automata (QCA) approach offers an attractive alternative to diode or transistor devices. Th units encode binary information by two polarizations without corrent flow. The units for QCA theory are called QCA cells and can be realized in several way. Molecules can act as QCA cells at room temperature. In collaboration with STMicroelectronic, the group of Electrochemistry of Prof. Paolucci and the Nananotecnology laboratory from Lecce, we synthesized and studied with many techniques surface-active chiral bis-ferrocenes, conveniently designed in order to act as prototypical units for molecular computing devices. The chemistry of ferrocene has been studied thoroughly and found the opportunity to promote substitution reaction of a ferrocenyl alcohols with various nucleophiles without the aid of Lewis acid as catalysts. The only interaction between water and the two reagents is involve in the formation of a carbocation specie which is the true reactive species. We have generalized this concept to other benzyl alcohols which generating stabilized carbocations. Carbocation describe in Mayr’s scale were fondametal for our research. Finally, we used these alcohols to alkylate in enantioselective way aldehydes via organocatalysis.
Resumo:
The main aims of my PhD research work have been the investigation of the redox, photophysical and electronic properties of carbon nanotubes (CNT) and their possible uses as functional substrates for the (electro)catalytic production of oxygen and as molecular connectors for Quantum-dot Molecular Automata. While for CNT many and diverse applications in electronics, in sensors and biosensors field, as a structural reinforcing in composite materials have long been proposed, the study of their properties as individual species has been for long a challenging task. CNT are in fact virtually insoluble in any solvent and, for years, most of the studies has been carried out on bulk samples (bundles). In Chapter 2 an appropriate description of carbon nanotubes is reported, about their production methods and the functionalization strategies for their solubilization. In Chapter 3 an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized individual single wall CNT (SWNT) is reported that permitted to determine for the first time the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also established the Fermi energy and the exciton binding energy for individual tubes in solution and, from the linear correlation found between the potentials and the optical transition energies, one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples. In Chapter 4 we report on very efficient and stable nano-structured, oxygen-evolving anodes (OEA) that were obtained by the assembly of an oxygen evolving polyoxometalate cluster, (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes (MWCNT). Here, MWCNT were effectively used as carrier of the polyoxometallate for the electrocatalytic production of oxygen and turned out to greatly increase both the efficiency and stability of the device avoiding the release of the catalysts. Our bioinspired electrode addresses the major challenge of artificial photosynthesis, i.e. efficient water oxidation, taking us closer to when we might power the planet with carbon-free fuels. In Chapter 5 a study on surface-active chiral bis-ferrocenes conveniently designed in order to act as prototypical units for molecular computing devices is reported. Preliminary electrochemical studies in liquid environment demonstrated the capability of such molecules to enter three indistinguishable oxidation states. Side chains introduction allowed to organize them in the form of self-assembled monolayers (SAM) onto a surface and to study the molecular and redox properties on solid substrates. Electrochemical studies on SAMs of these molecules confirmed their attitude to undergo fast (Nernstian) electron transfer processes generating, in the positive potential region, either the full oxidized Fc+-Fc+ or the partly oxidized Fc+-Fc species. Finally, in Chapter 6 we report on a preliminary electrochemical study of graphene solutions prepared according to an original procedure recently described in the literature. Graphene is the newly-born of carbon nanomaterials and is certainly bound to be among the most promising materials for the next nanoelectronic generation.
