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.

String inflationary models with non-monotonic slow-roll and detectable tensor modes

The first chapter of this work has the aim to provide a brief overview of the history of our Universe, in the context of string theory and considering inflation as its possible application to cosmological problems. We then discuss type IIB string compactifications, introducing the study of the inflaton, a scalar field candidated to describe the inflation theory. The Large Volume Scenario (LVS) is studied in the second chapter paying particular attention to the stabilisation of the Kähler moduli which are four-dimensional gravitationally coupled scalar fields which parameterise the size of the extra dimensions. Moduli stabilisation is the process through which these particles acquire a mass and can become promising inflaton candidates. The third chapter is devoted to the study of Fibre Inflation which is an interesting inflationary model derived within the context of LVS compactifications. The fourth chapter tries to extend the zone of slow-roll of the scalar potential by taking larger values of the field φ. Everything is done with the purpose of studying in detail deviations of the cosmological observables, which can better reproduce current experimental data. Finally, we present a slight modification of Fibre Inflation based on a different compactification manifold. This new model produces larger tensor modes with a spectral index in good agreement with the date released in February 2015 by the Planck satellite.

Dynamical Casimir effect and the structure of vacuum in quantum field theory

Some of the most interesting phenomena that arise from the developments of the modern physics are surely vacuum fluctuations. They appear in different branches of physics, such as Quantum Field Theory, Cosmology, Condensed Matter Physics, Atomic and Molecular Physics, and also in Mathematical Physics. One of the most important of these vacuum fluctuations, sometimes called "zero-point energy", as well as one of the easiest quantum effect to detect, is the so-called Casimir effect. The purposes of this thesis are: - To propose a simple retarded approach for dynamical Casimir effect, thus a description of this vacuum effect when we have moving boundaries. - To describe the behaviour of the force acting on a boundary, due to its self-interaction with the vacuum.

Exploiting the clustering of cosmic voids as a novel cosmological probe

The investigations of the large-scale structure of our Universe provide us with extremely powerful tools to shed light on some of the open issues of the currently accepted Standard Cosmological Model. Until recently, constraining the cosmological parameters from cosmic voids was almost infeasible, because the amount of data in void catalogues was not enough to ensure statistically relevant samples. The increasingly wide and deep fields in present and upcoming surveys have made the cosmic voids become promising probes, despite the fact that we are not yet provided with a unique and generally accepted definition for them. In this Thesis we address the two-point statistics of cosmic voids, in the very first attempt to model its features with cosmological purposes. To this end, we implement an improved version of the void power spectrum presented by Chan et al. (2014). We have been able to build up an exceptionally robust method to tackle with the void clustering statistics, by proposing a functional form that is entirely based on first principles. We extract our data from a suite of high-resolution N-body simulations both in the LCDM and alternative modified gravity scenarios. To accurately compare the data to the theory, we calibrate the model by accounting for a free parameter in the void radius that enters the theory of void exclusion. We then constrain the cosmological parameters by means of a Bayesian analysis. As far as the modified gravity effects are limited, our model is a reliable method to constrain the main LCDM parameters. By contrast, it cannot be used to model the void clustering in the presence of stronger modification of gravity. In future works, we will further develop our analysis on the void clustering statistics, by testing our model on large and high-resolution simulations and on real data, also addressing the void clustering in the halo distribution. Finally, we also plan to combine these constraints with those of other cosmological probes.

An introduction to scalar-tensor gravity: theory and experiment in the Brans-Dicke model

Le teorie della gravità scalare-tensore sono una classe di teorie alternative alla rel- atività generale in cui l’interazione gravitazionale è descritta sia dalla metrica, sia da un campo scalare. Ne costituisce un esempio caratteristico la teoria di Brans-Dicke, in- trodotta come estensione della relatività generale in modo da renderla conforme con il principio di Mach. Il presente lavoro di tesi è volto a presentare un’analisi di questa teoria nei suoi aspetti principali, studiandone i fondamenti teorici e il modello cosmologico derivante, sottolineandone inoltre i limiti e le criticità; in seguito vengono esposti i risultati degli esperimenti fino ad ora svolti per verificare fondamenti e previsioni del modello.