In-situ DRIFT/MS study of the conversion of ethanol on mixed Mg/Si oxides

Due to the high price of natural oil and harmful effects of its usage, as the increase in emission of greenhouse gases, the industry focused in searching of sustainable types of the raw materials for production of chemicals. Ethanol, produced by fermentation of sugars, is one of the more interesting renewable materials for chemical manufacturing. There are numerous applications for the conversion of ethanol into commodity chemicals. In particular, the production of 1,3-butadiene whose primary source is ethanol using multifunctional catalysts is attractive. With the 25% of world rubber manufacturers utilizing 1,3-butadiene, there is an exigent need for its sustainable production. In this research, the conversion of ethanol in one-step process to 1,3-butadiene was studied. According to the literature, the mechanisms which were proposed to explain the way ethanol transforms into butadiene require to have both acid and basic sites. But still, there are a lot of debate on this topic. Thus, the aim of this research work is a better understanding of the reaction pathways with all the possible intermediates and products which lead to the formation of butadiene from ethanol. The particular interests represent the catalysts, based on different ratio Mg/Si in comparison to bare magnesia and silica oxides, in order to identify a good combination of acid/basic sites for the adsorption and conversion of ethanol. Usage of spectroscopictechniques are important to extract information that could be helpful for understanding the processes on the molecular level. The diffuse reflectance infrared spectroscopy coupled to mass spectrometry (DRIFT-MS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Whereas, mass spectrometry was used to monitor the desorbed products. The set of studied materials include MgO, Mg/Si=0.1, Mg/Si=2, Mg/Si=3, Mg/Si=9 and SiO2 which were also characterized by means of surface area measurements.

Organic/inorganic polyoxometalate-based hybrids for oxidation catalysis and energy conversion

This thesis work has been carried out during the Erasmus exchange period at the “Université Paris 6 – Pierre et Marie Curie”, in the “Edifices PolyMétalliques – EPOM” team, leaded by Prof. Anna Proust, belonging to the “Institut Parisien de Chimie Moléculaire”, under the supervision of Dr. Guillaume Izzet and Dr. Geoffroy Guillemot. The redox properties of functionalized Keggin and Dawson POMs have been exploited in photochemical, catalytic and reactivity tests. For the photochemical purposes, the selected POMs have been functionalized with different photoactive FGs, and the resulting products have been characterized by CV analyses, luminescence tests and UV-Vis analyses. In future, these materials will be tested for hydrogen photoproduction and polymerization of photoactive films. For the catalytic purposes, POMs have been firstly functionalized with silanol moieties, to obtain original coordination sites, and then post-functionalized with TMs such as V, Ti and Zr in their highest oxidation states. In this way, the catalytic properties of TMs were coupled to the redox properties of POM frameworks. The redox behavior of some of these hybrids has been studied by spectro-electrochemical and EPR methods. Catalytic epoxidation tests have been carried out on allylic alcohols and n-olefins, employing different catalysts and variable amounts of them. The performances of POM-V hybrids have been compared to those of VO(iPrO)3. Finally, reactivity of POM-VIII hybrids has been studied, using styrene oxide and ethyl-2-diazoacetate as substrates. All the obtained products have been analyzed via NMR techniques. Cyclovoltammetric analyses have been carried out in order to determine the redox behavior of selected hybrids.

Ultra low power analog-to-information conversion by short-time compressed sensing

Il compressed sensing è un’innovativa tecnica per l’acquisizione dei dati, che mira all'estrazione del solo contenuto informativo intrinseco di un segnale. Ciò si traduce nella possibilità di acquisire informazione direttamente in forma compressa, riducendo la quantità di risorse richieste per tale operazione. In questa tesi è sviluppata un'architettura hardware per l'acquisizione di segnali analogici basata sul compressed sensing, specializzata al campionamento con consumo di potenza ridotto di segnali biomedicali a basse frequenze. Lo studio è svolto a livello di sistema mediante l'integrazione della modulazione richiesta dal compressed sensing in un convertitore analogico-digitale ad approssimazioni successive, modificandone la logica di controllo. Le prestazioni risultanti sono misurate tramite simulazioni numeriche e circuitali. Queste confermano la possibilità di ridurre la complessità hardware del sistema di acquisizione rispetto allo stato dell'arte, senza alterarne le prestazioni.

CFD Applications for Wave Energy Conversion Devices (MoonWEC) and Turbulent Fountains for Environmental Fluid Mechanics

This thesis is based on two studies that are related to floating wave energy conversion (WEC) devices and turbulent fountains. The ability of the open-source CFD software OpenFOAM® has been studied to simulate these phenomena. The CFD model has been compared with the physical experimental results. The first study presents a model of a WEC device, called MoonWEC, which is patented by the University of Bologna. The CFD model of the MoonWEC under the action of waves has been simulated using OpenFOAM and the results are promising. The reliability of the CFD model is confirmed by the laboratory experiments, conducted at the University of Bologna, for which a small-scale prototype of the MoonWEC was made from wood and brass. The second part of the thesis is related to the turbulent fountains which are formed when a heavier source fluid is injected upward into a lighter ambient fluid, or else a lighter source fluid is injected downward into a heavier ambient fluid. For this study, the first case is considered for laboratory experiments and the corresponding CFD model. The vertical releases of the source fluids into a quiescent, uniform ambient fluid, from a circular source, were studied with different densities in the laboratory experiments, conducted at the University of Parma. The CFD model has been set up for these experiments. Favourable results have been observed from the OpenFOAM simulations for the turbulent fountains as well, indicating that it can be a reliable tool for the simulation of such phenomena.

Voice conversion with pre-trained representations for audio anonymization

The recording and processing of voice data raises increasing privacy concerns for users and service providers. One way to address these issues is to move processing on the edge device closer to the recording so that potentially identifiable information is not transmitted over the internet. However, this is often not possible due to hardware limitations. An interesting alternative is the development of voice anonymization techniques that remove individual speakers characteristics while preserving linguistic and acoustic information in the data. In this work, a state-of-the-art approach to sequence-to-sequence speech conversion, ini- tially based on x-vectors and bottleneck features for automatic speech recognition, is explored to disentangle the two acoustic information using different pre-trained speech and speakers representation. Furthermore, different strategies for selecting target speech representations are analyzed. Results on public datasets in terms of equal error rate and word error rate show that good privacy is achieved with limited impact on converted speech quality relative to the original method.