Investigation on the role of polymeric ligands in heterogeneous nanocatalysis towards the development of hybrid metal-polymer catalysts

The relationship between catalytic properties and the nature of the active phase is well-established, with increased presence typically leading to enhanced catalysis. However, the costs associated with acquiring and processing these metals can become economically and environmentally unsustainable for global industries. Thus, there is potential for a paradigm shift towards utilizing polymeric ligands or other polymeric systems to modulate and enhance catalytic performance. This alternative approach has the potential to reduce the requisite amount of active phase while preserving effective catalytic activity. Such a strategy could yield substantial benefits from both economic and environmental perspectives. The primary objective of this research is to examine the influence of polymeric hydro-soluble ligands on the final properties, such as size and dispersion of the active phase, as well as the catalytic activity, encompassing conversion, selectivity towards desired products, and stability, of colloidal gold nanoparticles supported on active carbon. The goal is to elucidate the impact of polymers systematically, offering a toolbox for fine-tuning catalytic performances from the initial stages of catalyst design. Moreover, investigating the potential to augment conversion and selectivity in specific reactions through tailored polymeric ligands holds promise for reshaping catalyst preparation methodologies, thereby fostering the development of more economically sustainable materials.

Performance assessment of vehicular connectivity in hybrid electric vehicles for fuel and emissions reduction

Nowadays, the spreading of the air pollution crisis enhanced by greenhouse gases emission is leading to the worsening of global warming. Recently, several metropolitan cities introduced Zero-Emissions Zones where the use of the Internal Combustion Engine is forbidden to reduce localized pollutants emissions. This is particularly problematic for Plug-in Hybrid Electric Vehicles, which usually work in depleting mode. In order to address these issues, the present thesis presents a viable solution by exploiting vehicular connectivity to retrieve navigation data of the urban event along a selected route. The battery energy needed, in the form of a minimum State of Charge (SoC), is calculated by a Speed Profile Prediction algorithm and a Backward Vehicle Model. That value is then fed to both a Rule-Based Strategy, developed specifically for this application, and an Adaptive Equivalent Consumption Minimization Strategy (A-ECMS). The effectiveness of this approach has been tested with a Connected Hardware-in-the-Loop (C-HiL) on a driving cycle measured on-road, stimulating the predictions with multiple re-routings. However, even if hybrid electric vehicles have been recognized as a valid solution in response to increasingly tight regulations, the reduced engine load and the repeated engine starts and stops may reduce substantially the temperature of the exhaust after-treatment system (EATS), leading to relevant issues related to pollutant emission control. In this context, electrically heated catalysts (EHCs) represent a promising solution to ensure high pollutant conversion efficiency without affecting engine efficiency and performance. This work aims at studying the advantages provided by the introduction of a predictive EHC control function for a light-duty Diesel plug-in hybrid electric vehicle (PHEV) equipped with a Euro 7-oriented EATS. Based on the knowledge of future driving scenarios provided by vehicular connectivity, engine first start can be predicted and therefore an EATS pre-heating phase can be planned.

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.