Theoretical and experimental studies of gold catalysts for glucose oxidation

The glucaric acid (GLA) has been identified as a “top value-added chemical from biomass” that can be employed for many uses; for instance, it could be a precursor of adipic acid, a monomer of Nylon-6,6. GLA can be synthetized by the oxidation of glucose (GLU), passing through the intermediate gluconic acid (GLO). In recent years, a new process has been sought to obtain GLA in an economic and environmental sustainable way, in order to replace the current use of HNO3 as a stoichiometric oxidant, or electrocatalysis and biochemical synthesis, which show several disadvantages. Thereby, this work is focused on the study of catalysts based on gold nanoparticles supported on activated carbon for the oxidation reaction of GLU to GLA using O2 as an oxidant agent and NaOH as base. The sol-immobilization method leads us to obtain small and well dispersed nanoparticles, characterized by UV-Vis, XRD and TEM techniques. Repeating the reaction on different batches of catalyst, both the synthesis and the reaction were confirmed to be reproducible. The effect of the reaction time feeding GLO as reagent was studied: the results show that the conversion of GLO increases as the reaction time increases; however, the yields of GLA and others increase up to 1 hour, and then they remain constant. In order to obtain information on the catalytic mechanism at the atomistic level, a computational study based on density functional theory and atomistic modeling of the gold nano-catalyst were performed. Highly symmetric (icosahedral and cubo-octahedral) and distorted Au55 nanoparticles have been optimized along with Au(111) and Au(100) surfaces. Distorted structures were found to be more stable than symmetrical ones due to relativistic effects. On these various models the adsorptions of various species involved in the catalysis have been studied, including OH- species, GLU and GLO. The study carried out aims to provide a method for approaching to the study of nanoparticellary catalytic systems.

Mobile TuCSoN: theoretical and technological requirements for TuCSoN's porting over Android mobile devices

Communication and coordination are two key-aspects in open distributed agent system, being both responsible for the system’s behaviour integrity. An infrastructure capable to handling these issues, like TuCSoN, should to be able to exploit modern technologies and tools provided by fast software engineering contexts. Thesis aims to demonstrate TuCSoN infrastructure’s abilities to cope new possibilities, hardware and software, offered by mobile technology. The scenarios are going to configure, are related to the distributed nature of multi-agent systems where an agent should be located and runned just on a mobile device. We deal new mobile technology frontiers concerned with smartphones using Android operating system by Google. Analysis and deployment of a distributed agent-based system so described go first to impact with quality and quantity considerations about available resources. Engineering issue at the base of our research is to use TuCSoN against to reduced memory and computing capability of a smartphone, without the loss of functionality, efficiency and integrity for the infrastructure. Thesis work is organized on two fronts simultaneously: the former is the rationalization process of the available hardware and software resources, the latter, totally orthogonal, is the adaptation and optimization process about TuCSoN architecture for an ad-hoc client side release.

Bionanocomposites based on Plla, Pcl and montmorillonite: synthesis, characterization and crystallization

Poly(lactide) is one of the best candidate to replace conventional petroleum-based polymers, since it is biobased, biocompatible and biodegradable. However, commercial PLA materials typically have low crystallization rate resulting in long processing time and low production efficiency. In this work the effects of two nanofillers MMT30B and MMT30B-g-P(LA-co-CL) on the crystallization rate of neat PLA and PLA/PCL blend were investigated. MMT30B-g-P(LA-co-CL) was synthetized by in situ grafting reaction. The synthesis was carried in xylene at 140°C, upon the results of a screening. The grafted copolymers were evaluated by 1H-NMR ,ATR–IR and TGA. Solvent casted films were obtained by mixing MMT30B-g-P(LA-co-CL) at 5% (w/w) with neat PLA and PLA/PCL blend, comparing the properties with the corresponding blends with and without a 5% of (w/w) unmodified clay. SEM images on PLA based blends shows that MMT30B is aggregated into larger particles compared to MMT30B-g-P(LLA-co-CL). This behavior is correlated to the better exfoliation of MMT30B-g-P(LA-co-CL) clay layers. SEM images on PLA/PCL based blends exhibit the typical sea-island morphology, characteristic of immiscible blends. PLA is the matrix while PCL is finely dispersed in droplets. MMT30B does not reduce PCL droplets size, while MMT30B-g-P(LA-co-CL) reduces the size of PCL droplets. This means that MMT30B-g-P(LA-co-CL) can migrate to the PLA-PCL interface, acting as a compatibilizer. Non-isothermal DSC cooling scans show a fractionated crystallization of the PCL phase in PLA/PCL/MMT30B-g-P(LA-co-CL), confirming the compatibilizer effect of MMT30B-g-P(LA-co-CL). At the same timeMMT30B-g-P(LA-co-CL) can better nucleate the PLA phase, both in neat PLA and PLA/PCL blend, promoting the crystallization during the heating scans. In isothermal condition, both the nanofillers increase the crystallization rate of PLA phase in neat PLA, while in PLA/PCL blends the effect is covered by the nucleating effect of PCL.

Theoretical and experimental investigations on homologation of ethanol to butanol using a ruthenium-based catalyst

The mechanism of homologation of bioethanol to butanol and higher alcohols via the Guerbet reaction was computationally and experimentally investigated. The catalytic pathway involves a ruthenium-based complex and a base co-catalyst which work simultaneously. Due to selectivity issues, secondary products were formed and high competition between main pathway and side reactions was recorded. Herein, the overall catalytic mechanism for all the processes involved in was investigated, also considering the principal side reactions, using density functional theory (DFT) methods and experiments to confirm theoretical outcomes. Due to the complexity of the reaction network, kinetic simulations were established from DFT results, confirming experimental products distribution and giving insights into the factors governing the reaction mechanism.

Factors affecting the mission time of an autonomous mobile robot: a theoretical and experimental investigation

I vantaggi dell’Industria 4.0 hanno stravolto il manufacturing. Ma cosa vuol dire "Industria 4.0"? Essa è la nuova frontiera del manufacturing, basata su princìpi che seguono i passi avanti dei sistemi IT e della tecnologia. Dunque, i suoi pilastri sono: integrazione, verticale e orizzontale, digitalizzazione e automazione. L’Industria 4.0 coinvolge molte aree della supply chain, dai flussi informativi alla logistica. In essa e nell’intralogistica, la priorità è sviluppare dei sistemi di material handling flessibili, automatizzati e con alta prontezza di risposta. Il modello ideale è autonomo, in cui i veicoli fanno parte di una flotta le cui decisioni sono rese decentralizzate grazie all'alta connettività e alla loro abilità di collezionare dati e scambiarli rapidamente nel cloud aziendale.Tutto ciò non sarebbe raggiungibile se ci si affidasse a un comune sistema di trasporto AGV, troppo rigido e centralizzato. La tesi si focalizza su un tipo di material handlers più flessibile e intelligente: gli Autonomous Mobile Robots. Grazie alla loro intelligenza artificiale e alla digitalizzazione degli scambi di informazioni, interagiscono con l’ambiente per evitare ostacoli e calcolare il percorso ottimale. Gli scenari dell’ambiente lavorativo determinano perdite di tempo nel tragitto dei robot e sono queste che dovremo studiare. Nella tesi, i vantaggi apportati dagli AMR, come la loro decentralizzazione delle decisioni, saranno introdotti mediante una literature review e poi l’attenzione verterà sull’analisi di ogni scenario di lavoro. Fondamentali sono state le esperienze nel Logistics 4.0 Lab di NTNU, per ricreare fisicamente alcuni scenari. Inoltre, il software AnyLogic sarà usato per riprodurre e simulare tutti gli scenari rilevanti. I risultati delle simulazioni verranno infine usati per creare un modello che associ ad ogni scenario rilevante una perdita di tempo, attraverso una funzione. Per questo saranno usati software di data analysis come Minitab e MatLab.

Theoretical and experimental study on the role of benzoquinone in the Guerbet reaction catalyzed by a ruthenium complex

The benzoquinone was found as an effective co-catalyst in the ruthenium/NaOEt-catalyzed Guerbet reaction. The co-catalyst behavior has therefore been investigated through experimental and computational methods. The reaction products distribution shows that the reaction speed is improved by the benzoquinone supplement since the beginning of the process, having a minimal effect on the selectivity toward alcoholic species. DFT calculations were performed to investigate two hypotheses for the kinetic effects: i) a hydrogen storage mechanism or ii) a basic co-catalysis of 4-hydroxiphenolate. The most promising results were found for the latter hypothesis, where a new mixed mechanism for the aldol condensation step of the Guerbet process involves the hydroquinone (i.e. the reduced form of benzoquinone) as proton source instead of ethanol. This mechanism was found to be energetically more favorable than an aldol condensation in absence of additive, suggesting that the hydroquinone derived from benzoquinone could be the key species affecting the kinetics of the overall process. To verify this theoretical hypothesis, new phenol derivatives were tested as additives in the Guerbet reaction. The outcomes confirmed that an aromatic acid (stronger than ethanol) could improve the reaction kinetics. Lastly, theoretical products distributions were simulated and compared to the experimental one, using the DFT computations to build the kinetic models.

Neural Radiance Fields for Relighting and View Synthesis

Neural scene representation and neural rendering are new computer vision techniques that enable the reconstruction and implicit representation of real 3D scenes from a set of 2D captured images, by fitting a deep neural network. The trained network can then be used to render novel views of the scene. A recent work in this field, Neural Radiance Fields (NeRF), presented a state-of-the-art approach, which uses a simple Multilayer Perceptron (MLP) to generate photo-realistic RGB images of a scene from arbitrary viewpoints. However, NeRF does not model any light interaction with the fitted scene; therefore, despite producing compelling results for the view synthesis task, it does not provide a solution for relighting. In this work, we propose a new architecture to enable relighting capabilities in NeRF-based representations and we introduce a new real-world dataset to train and evaluate such a model. Our method demonstrates the ability to perform realistic rendering of novel views under arbitrary lighting conditions.

Circumplex Model to analyze the impact of emotions on decision-making processes in innovation management

Group work allows participants to pool their thoughts and examine difficulties from several angles. In these settings, it is possible to attempt things that an individual could not achieve, combining a variety of abilities and knowledge to tackle more complicated and large-scale challenges. That’s why nowadays collaborative work is becoming more and more widespread to solve complex innovation dilemmas. Since innovation isn’t a tangible thing, most innovation teams used to take decisions based on performance KPIs such as forecasted engagement, projected profitability, investments required, cultural impacts etc. Have you ever wondered the reason why sometimes innovation group processes come out with decisions which are not the optimal meeting point of all the KPIs? Has this decision been influenced by other factors? Some researchers account part of this phenomenon to the emotions in group-based interaction between participants. I will develop a literature review that is split into three parts: first, I will consider some emotions theories from an individual perspective; secondly, a wider view of collective interactions theories will be provided; lastly, I will supply some recent collective interaction empirical studies. After the theoretical and empirical gaps have been tackled, the study will additionally move forward with a methodological point of view, about the Circumplex Model, which is the model I used to evaluate emotions in my research. This model has been applied to SUGAR project, which is the biggest design thinking academy worldwide.