Strategies and procedures for the development of intermodal freight transport in Europe: the role of motorways of the sea services and railway terminals

Since the birth of the European Union on 1957, the development of a single market through the integration of national freight transport networks has been one of the most important points in the European Union agenda. Increasingly congested motorways, rising oil prices and concerns about environment and climate change require the optimization of transport systems and transport processes. The best solution should be the intermodal transport, in which the most efficient transport options are used for the different legs of transport. This thesis examines the problem of defining innovative strategies and procedures for the sustainable development of intermodal freight transport in Europe. In particular, the role of maritime transport and railway transport in the intermodal chain are examined in depth, as these modes are recognized to be environmentally friendly and energy efficient. Maritime transport is the only mode that has kept pace with the fast growth in road transport, but it is necessary to promote the full exploitation of it by involving short sea shipping as an integrated service in the intermodal door-to-door supply chain and by improving port accessibility. The role of Motorways of the Sea services as part of the Trans-European Transport Network is is taken into account: a picture of the European policy and a state of the art of the Italian Motorways of the Sea system are reported. Afterwards, the focus shifts from line to node problems: the role of intermodal railway terminals in the transport chain is discussed. In particular, the last mile process is taken into account, as it is crucial in order to exploit the full capacity of an intermodal terminal. The difference between the present last mile planning models of Bologna Interporto and Verona Quadrante Europa is described and discussed. Finally, a new approach to railway intermodal terminal planning and management is introduced, by describing the case of "Terminal Gate" at Verona Quadrante Europa. Some proposals to favour the integrate management of "Terminal Gate" and the allocation of its capacity are drawn up.

Analysis of the Slow Food movement impact on the farmers and rural areas’ sustainable development

The evaluation of the farmers’ communities’ approach to the Slow Food vision, their perception of the Slow Food role in supporting their activity and their appreciation and expectations from participating in the event of Mother Earth were studied. The Unified Theory of Acceptance and Use of Technology (UTAUT) model was adopted in an agro-food sector context. A survey was conducted, 120 questionnaires from farmers attending the Mother Earth in Turin in 2010 were collected. The descriptive statistical analysis showed that both Slow Food membership and participation to Mother Earth Meeting were much appreciated for the support provided to their business and the contribution to a more sustainable and fair development. A positive social, environmental and psychological impact on farmers also resulted. Results showed also an interesting perspective on the possible universality of the Slow Food and Mother Earth values. Farmers declared that Slow Food is supporting them by preserving the biodiversity and orienting them to the use of local resources and reducing the chemical inputs. Many farmers mentioned the language/culture and administration/bureaucratic issues as an obstacle to be a member in the movement and to participate to the event. Participation to Mother Earth gives an opportunity to exchange information with other farmers’ communities and to participate to seminars and debates, helpful for their business development. The absolute majority of positive answers associated to the farmers’ willingness to relate to Slow Food and participate to the next Mother Earth editions negatively influenced the UTAUT model results. A factor analysis showed that the variables associated to the UTAUT model constructs Performance Expectancy and Effort Expectancy were consistent, able to explain the construct variability, and their measurement reliable. Their inclusion in a simplest Technology Acceptance Model could be considered in future researches.

Development of methodologies supporting the sustainable and safe integration of offshore conventional and renewable energy production

Against a backdrop of rapidly increasing worldwide population and growing energy demand, the development of renewable energy technologies has become of primary importance in the effort to reduce greenhouse gas emissions. However, it is often technically and economically infeasible to transport discontinuous renewable electricity for long distances to the shore. Another shortcoming of non-programmable renewable power is its integration into the onshore grid without affecting the dispatching process. On the other hand, the offshore oil & gas industry is striving to reduce overall carbon footprint from onsite power generators and limiting large expenses associated to carrying electricity from remote offshore facilities. Furthermore, the increased complexity and expansion towards challenging areas of offshore hydrocarbons operations call for higher attention to safety and environmental protection issues from major accident hazards. Innovative hybrid energy systems, as Power-to-Gas (P2G), Power-to-Liquid (P2L) and Gas-to-Power (G2P) options, implemented at offshore locations, would offer the opportunity to overcome challenges of both renewable and oil & gas sectors. This study aims at the development of systematic methodologies based on proper sustainability and safety performance indicators supporting the choice of P2G, P2L and G2P hybrid energy options for offshore green projects in early design phases. An in-depth analysis of the different offshore hybrid strategies was performed. The literature reviews on existing methods proposing metrics to assess sustainability of hybrid energy systems, inherent safety of process routes in conceptual design stage and environmental protection of installations from oil and chemical accidental spills were carried out. To fill the gaps, a suite of specific decision-making methodologies was developed, based on representative multi-criteria indicators addressing technical, economic, environmental and societal aspects of alternative options. A set of five case-studies was defined, covering different offshore scenarios of concern, to provide an assessment of the effectiveness and value of the developed tools.

Design and development of new green catalytic methodologies for the synthesis of enantiomerically enriched molecules

The following Ph.D work was mainly focused on catalysis, as a key technology, to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and an assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry was briefly discussed and illustrated via an analysis of some selected and relevant examples. Afterwards, as a continuation of the ongoing interest in Dr. Marco Bandini’s group on organometallic and organocatalytic processes, I addressed my efforts to the design and development of novel catalytic green methodologies for the synthesis of enantiomerically enriched molecules. In the first two projects the attention was focused on the employment of solid supports to carry out reactions that still remain a prerogative of omogeneous catalysis. Firstly, particular emphasis was addressed to the discovery of catalytic enantioselective variants of nitroaldol condensation (commonly termed Henry reaction), using a complex consisting in a polyethylene supported diamino thiopene (DATx) ligands and copper as active species. In the second project, a new class of electrochemically modified surfaces with DATx palladium complexes was presented. The DATx-graphite system proved to be efficient in promoting the Suzuki reaction. Moreover, in collaboration with Prof. Wolf at the University of British Columbia (Vancouver), cyclic voltammetry studies were reported. This study disclosed new opportunities for carbon–carbon forming processes by using heterogeneous, electrodeposited catalyst films. A straightforward metal-free catalysis allowed the exploration around the world of organocatalysis. In fact, three different and novel methodologies, using Cinchona, Guanidine and Phosphine derivatives, were envisioned in the three following projects. An interesting variant of nitroaldol condensation with simple trifluoromethyl ketones and also their application in a non-conventional activation of indolyl cores by Friedel-Crafts-functionalization, led to two novel synthetic protocols. These approaches allowed the preparation of synthetically useful trifluoromethyl derivatives bearing quaternary stereocenters. Lastly, in the sixth project the first γ-alkylation of allenoates with conjugated carbonyl compounds was envisioned. In the last part of this Ph.D thesis bases on an extra-ordinary collaboration with Prof. Balzani and Prof. Gigli, I was involved in the synthesis and characterization of a new type of heteroleptic cyclometaled-Ir(III) complexes, bearing bis-oxazolines (BOXs) as ancillary ligands. The new heteroleptic complexes were fully characterized and in order to examine the electroluminescent properties of FIrBOX(CH2), an Organic Light Emitting Device was realized.

Development of innovative catalysts for the hydrodechlorination to fluoroethers

In this work the hydrodechlorination of CF3OCFClCF2Cl to produce unsaturated CF3OCF=CF2 was studied over a series of supported metal catalysts. Currently this molecule is produced from the precursor CF3OCFClCF2Cl by dechlorination with zinc powder. An important cost on the economic and environmental balance is represents by the large amount of ZnCl2 produced and to be disposed of. A new approach, based on gas-phase hydrodechlorination over supported catalysts can lead to a new sustainable process. During the feasibility step of this project, substantially two kind of materials were studied: metals supported over activated carbon and Pd/Cu species supported over MCM-41 mesoporous silica. Observed catalytic performances were strongly dependent on the metal and support used. All carbon-supported Ru, Pd, and bimetallic catalysts are fairly active and yielded the target product CF3OCF=CF2, the higher selectivity being obtained with ruthenium- and palladium-based materials. Nevertheless, Ru-based catalysts showed poor stability and this deactivation may be attributed to the deposition of chlorinated organic species blocking the active sites. On the other hand, palladium-containing catalysts showed high stability. Ru/Pd and Pd/Cu bimetallic catalysts exhibited long-term selectivity and stability, highlighting the possibility for these materials to be employed in the CF3OCF=CF2 production process. During the second part of this thesis, a series of bimetallic meso-structured Pd/Cu MCM-41 catalysts were studies to overcome possible mass transfer limitations. The materials were obtained by different synthesis methods. The incorporation of Pd and Cu during MCM-41 synthesis, did not destroy the typical hexagonal array and ordered pore system of MCM-41. However, the calcination for the removal of the template provoked significant segregation of oxides. The impregnation leads to pore-occlusion and formation of Cu particles and large bimetallic PdCu species. Larger metal particles leads to lower CF3OCFClCF2Cl conversion, while the monometallic particles can decrease the selectivity to CF3OCF=CF2, fostering the dehalogenation to CF3OCH=CF2.

Development of an innovative pyrolysis plant for the production of secondary raw materials

This project was born with the aim of developing an environmentally and financially sustainable process to dispose of end-life tires. In this perspective was devised an innovative static bed batch pilot reactor where pyrolysis can be carried out on the whole tires in order to recover energy and materials and simultaneously save the energy costs of their shredding. The innovative plant is also able to guarantee a high safety of the process thanks to the presence of a hydraulic guard. The pilot plant was used to pyrolyze new and end-life tires at temperatures from 400 to 600°C with step of 50°C in presence of steam. The main objective of this research was to evaluate the influence of the maximum process temperature on yields and chemical-physics properties of pyrolysis products. In addition, in view of a scale-up of the plant in continuous mode, the influence of the nature of several different tires as well as the effects of the aging on the final products were studied. The same pilot plant was also used to carry out pyrolysis on polymeric matrix composites in order to obtain chemical feedstocks from the resin degradation together with the recovery of the reinforcement in the form of fibers. Carbon fibers reinforced composites ad fiberglass was treated in the 450-600°C range and the products was fully characterized. A second oxidative step was performed on the pyrolysis solid residue in order to obtain the fibers in a suitable condition for a subsequent re-impregnation in order to close the composite Life Cycle in a cradle-to-cradle approach. These investigations have demonstrated that steel wires, char, carbon and glass fibers recovered in the prototypal plant as solid residues can be a viable alternative to pristine materials, making use of them to obtain new products with a commercial added value.

Development of Advanced Combustions using Cylinder Pressure Signal

Zero-carbon powertrains development has become one of the main challenges for automotive industries around the world. Following this guideline, several approaches such as powertrain electrification, advanced combustions, and hydrogen internal combustion engines have been aimed to achieve the goal. Low Temperature Combustions, characterized by a simultaneous reduction of fuel consumption and emissions, represent one of the most studied solutions moving towards a sustainable mobility. Previous research demonstrate that Gasoline partially premixed Compression Ignition combustion is one of the most promising LTC. Mainly characterized by the high-pressure direct-injection of gasoline and the spontaneous ignition of the premixed air-fuel mixture, GCI combustion has shown a good potential to achieve the high thermal efficiency and low pollutants in compression ignited engines required by future emission regulations. Despite its potential, GCI combustion might suffer from low combustion controllability and stability, because gasoline spontaneous ignition is significantly affected by slight variations of the local in-cylinder thermal conditions. Therefore, to properly control GCI combustion assuring the maximum performance, a deep knowledge of the combustion process, i.e., gasoline auto-ignition and the effect of the control parameters on the combustion and pollutants, is mandatory. This PhD dissertation focuses on the study of GCI combustion in a light-duty compression ignited engine. Starting from a standard 1.3L diesel engine, this work describes the activities made moving toward the full conversion of the engine. A preliminary study of the GCI combustion was conducted in a “Single-Cylinder” engine configuration highlighting combustion characteristics and dependencies on the control parameters. Then, the full engine conversion was performed, and a wide experimental campaign allowed to confirm the benefits of this advanced combustion methodologies in terms of pollutants and thermal efficiency. The analysis of the in-cylinder pressure signal allowed to study in depth the GCI combustion and develop control-oriented models aimed to improve the combustion stability.

Untangle sustainable development goal 8 through data visualization and HCI methods

Following the approval of the 2030 Agenda for Sustainable Development in 2015, sustainability became a hotly debated topic. In order to build a better and more sustainable future by 2030, this agenda addressed several global issues, including inequality, climate change, peace, and justice, in the form of 17 Sustainable Development Goals (SDGs), that should be understood and pursued by nations, corporations, institutions, and individuals. In this thesis, we researched how to exploit and integrate Human-Computer Interaction (HCI) and Data Visualization to promote knowledge and awareness about SDG 8, which wants to encourage lasting, inclusive, and sustainable economic growth, full and productive employment, and decent work for all. In particular, we focused on three targets: green economy, sustainable tourism, employment, decent work for all, and social protection. The primary goal of this research is to determine whether HCI approaches may be used to create and validate interactive data visualization that can serve as helpful decision-making aids for specific groups and raise their knowledge of public-interest issues. To accomplish this goal, we analyzed four case studies. In the first two, we wanted to promote knowledge and awareness about green economy issues: we investigated the Human-Building Interaction inside a Smart Campus and the dematerialization process inside a University. In the third, we focused on smart tourism, investigating the relationship between locals and tourists to create meaningful connections and promote more sustainable tourism. In the fourth, we explored the industry context to highlight sustainability policies inside well-known companies. This research focuses on the hypothesis that interactive data visualization tools can make communities aware of sustainability aspects related to SDG8 and its targets. The research questions addressed are two: "how to promote awareness about SDG8 and its targets through interactive data visualizations?" and "to what extent are these interactive data visualizations effective?".

Green approach to Palladium Cross-Coupling reactions and development of new methodologies based on highly abundant metals

Transition metal catalyzed cross-coupling reactions represent among the most versatile and useful tools in organic synthesis for the carbon-carbon (C-C) bond formation and have a prominent role in both the academic and pharmaceutical segments. Among them, palladium catalyzed cross-coupling reactions are currently the most versatile. In this thesis, the applications, impact and development of green palladium cross-coupling reactions are discussed. Specifically, we discuss the translation of the Twelve Principles of Green Chemistry and their applications in pharmaceutical organometallic chemistry to stimulate the development of cost-effective and sustainable catalytic processes for the synthesis of active pharmaceutical ingredients (API). The Heck-Cassar-Sonogashira (HCS) and the Suzuki-Miyaura (SM) protocols, using HEP/H2O as green mixture and sulfonated phosphine ligands, allowed to recycle and recover the catalyst, always guaranteeing high yields and fast conversion under mild conditions, with aryl iodides, bromides, triflates and chlorides. No catalyst leakage or metal contamination of the final product were observed during the HCS and SM reactions, respecting the very low limits for metal impurities in medicines established by the International Conference of Harmonization Guidelines Q3D (ICH Q3D). In addition, a deep understanding of the reaction mechanism is very important if the final target is to develop efficient protocols that can be applied at industrial level. Experimental and theoretical studies pointed out the presence of two catalytic cycles depending on the counterion, shedding light on the role of base in catalyst reduction and acetylene coordination in the HCS coupling. Finally, the development of a cross-coupling reaction to form aryldifluoronitriles in the presence of copper is discussed, highlighting the importance of inserting fluorine atoms within biological structures and the use of readily available metals such as copper as an alternative to palladium.

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.