Nonaqueous sol-gel routes to doped metal oxide nanoparticles: synthesis, characterization, assembly and properties

The results presented in this thesis have been achieved under the Ph.D. project entitled “Nonaqueous Sol-Gel routes to doped metal oxide nanoparticles: Synthesis, characterization, assembly and properties”. The purpose of this study is the investigation of metal oxide nanostructures doped with metals of a diverse nature, leading to different type of applications. The easier control over the reaction kinetics in solvothermal routes, compared to aqueous methods, allows to better match the reactivity between metal oxide precursors, paving the way to a facile and low temperature production of doped oxides. In this manuscript diverse examples of the exploitation of the “Benzyl Alcohol Route” are discussed. Such a powerful pathway was utilized for the synthesis of transition metal doped zirconia, hafnia and various perovskites, and the study of their magnetic properties, as well as the synthesis of rare earth doped zirconium oxide. A further extension, proving the solidity of the synthetic method, is shown for the preparation of Li4Ti5O12 nanocrystals carrying excellent electrochemical properties for lithium-ion battery applications. Finally, the effect of doping and other reaction parameters on the assembly of the nanocrystals is discussed. These studies were carried out principally at the University of Aveiro, as well as at the University of Montpellier II and at the Seoul National University due to complementary available expertises and equipments.

Catalytic routes to convert saccharides to furanic aldehydes

The conversion of plant biomass-derived carbohydrates (preferably non-edible) into added-value products is envisaged to be at the core of the future biorefineries. Carbohydrates are the most abundant natural organic polymers on Earth. This work deals with the chemical valorisation of plant biomass, focusing on the acid-catalysed conversion of carbohydrates (mono and polysaccharides) to furanic aldehydes, namely 2-furaldehyde (Fur) and 5-hydroxymethyl-2-furaldehyde (Hmf), which are valuable platform chemicals that have the potential to replace a variety of oil derived chemicals and materials. The investigated reaction systems can be divided into two types depending on the solvent used to dissolve the carbohydrates in the reaction medium: water or ionic liquid-based systems. The reaction temperatures were greater than 150 ºC when the solvent was water, and lower than 150 º C in the cases of the ionic liquid-based catalytic systems. As alternatives to liquid acids (typically used in the industrial production of Fur), solid acid catalysts were investigated in these reaction systems. Aiming at the identification of (soluble and insoluble) reaction products, complementary characterisation techniques were used namely, FT-IR spectroscopy, liquid and solid state NMR spectroscopy, TGA, DSC and GC´GC-ToFMS analyses. Complex mixtures of soluble reaction products were obtained and different types of side reactions may occur. The requirements to be put on the catalysts for these reaction systems partly depend on the type of carbohydrates to be converted and the reaction conditions used. The thermal stability is important due to the fact that formation of humins and catalyst coking phenomena are characteristically inherent to these types of reactions systems leading to the need to regenerate the catalyst which can be effectively accomplished by calcination. Special attention was given to fully inorganic nanoporous solid acids, amorphous or crystalline, and consisting of nano to micro-size particles. The investigated catalysts were silicoaluminophosphates, aluminosilicates and zirconium-tungsten mixed oxides which are versatile catalysts in that their physicochemical properties can be fine-tuned to improve the catalytic performances in the conversion of different substrates (e.g. introduction of mesoporosity and modification of the acid properties). The catalytic systems consisting of aluminosilicates as solid acids and water as solvent seem to be more effective in converting pentoses and related polysaccharides into Fur, than hexoses and related polysaccharides into Hmf. The investigated solid acids exhibited fairly good hydrothermal stabilities. On the other hand, ionic liquid-based catalytic systems can allow reaching simultaneously high Fur and Hmf yields, particularly when Hmf is obtained from D-fructose and related polysaccharides; however, catalyst deactivation occurs and the catalytic reactions take place in homogeneous phase. As pointed out in a review of the state of the art on this topic, the development of truly heterogeneous ionic liquid-based catalytic systems for producing Fur and Hmf in high yields remains a challenge.

Unusual reactivity of selenoboranes towards epoxides: New selective routes to beta- hydroxyselenides and allylalcohols

Selenoboranes react with terminal, α, β-di- and trisubstituted epoxides to produce β-hydroxyselenides (or olefins) in the two first cases and allyl alcohols in the last one. A very high stereodescrimination has been observed for α, β-bisubstituted epoxides: the cis epoxide being much more reactive.

Empathic and non-empathic routes to visuospatial perspective-taking

The present study examined whether strategy moderated the relationship between visuospatial perspective-taking and empathy. Participants (N=96) undertook both a perspective-taking task requiring speeded spatial judgements made from the perspective of an observed figure and the Empathy Quotient questionnaire, a measure of trait empathy. Perspective-taking performance was found to be related to empathy in that more empathic individuals showed facilitated performance particularly for figures sharing their own spatial orientation. This relationship was restricted to participants that reported perspective-taking by mentally transforming their spatial orientation to align with that of the figure; it was absent in those adopting an alternative strategy of transposing left and right whenever confronted with a front-view figure. Our finding that strategy moderates the relationship between empathy and visuospatial perspective-taking enables a reconciliation of the apparently inconclusive findings of previous studies and provides evidence for functionally dissociable empathic and non-empathic routes to visuospatial perspective-taking.

Genetic algorithm for shipping route estimation with long-range tracking data : automatic reconstruction of shipping routes based on the historical ship positions for maritime safety applications

Ship tracking systems allow Maritime Organizations that are concerned with the Safety at Sea to obtain information on the current location and route of merchant vessels. Thanks to Space technology in recent years the geographical coverage of the ship tracking platforms has increased significantly, from radar based near-shore traffic monitoring towards a worldwide picture of the maritime traffic situation. The long-range tracking systems currently in operations allow the storage of ship position data over many years: a valuable source of knowledge about the shipping routes between different ocean regions. The outcome of this Master project is a software prototype for the estimation of the most operated shipping route between any two geographical locations. The analysis is based on the historical ship positions acquired with long-range tracking systems. The proposed approach makes use of a Genetic Algorithm applied on a training set of relevant ship positions extracted from the long-term storage tracking database of the European Maritime Safety Agency (EMSA). The analysis of some representative shipping routes is presented and the quality of the results and their operational applications are assessed by a Maritime Safety expert.

Sciences appliquées à l'art militaire : chemins de fer, télégraphie électrique et optique, téléphonie, pigeons voyageurs, aérostation, ponts militaires, routes militaires

Collection : Encyclopédie théorique et pratique des connaissances civiles et militaires ; partie 2, livre 6