Mesoporous Carbon as effective and sustainable catalyst for fine chemistry

It is well known that activated carbon with welldeveloped porosity is a promising material that have been used for several applications, from adsorption to catalysis. Research in this field has intensified in recent years, looking for new and improved characteristics and applications. Our research group, recently renamed Materials for Adsorption and Catalysis group (MAC) in LAQV-REQUIMTE, has also devoted many research work in this subject, and has developed several collaboration works with other national and international research groups in the field. Among our research group interests there is the study of catalytic properties of carbon materials and specifically mesoporous carbon. Some of the promising results were selected and summarized here, demonstrating that mesoporous carbon is an efficient and environmentally friendly heterogeneous catalyst.

First report on Meloidogyne chitwoodi hatching inhibition activity of essential oils and essential oils fractions

The Columbia root-knot nematode (CRKN), Meloidogyne chitwoodi, is an EPPO A2 type quarantine pest since 1998. This nematode causes severe damage in economically important crops such as potato and tomato, making agricultural products unacceptable for the fresh market and food processing. Commonly used nematicidal synthetic chemicals are often environmentally unsafe. Essential oils (EOs) may constitute safer alternatives against RKN. EOs, isolated from 56 plant samples, were tested against CRKN hatching, in direct contact bioassays. Some of the most successful EOs were fractionated and the hydrocarbon molecules (HM) and oxygen-containing molecules (OCM) fractions tested separately. 24 EOs displayed very strong hatching inhibitions (≥90 %) at 2 µL mL−1 and were further tested at lower concentrations. Dysphaniaambrosioides, Filipendula ulmaria, Ruta graveolens, Satureja montana and Thymbra capitata EOs revealed the lowest EC50 values (<0.15 µL mL−1). The main compounds of these EOs, namely 2-undecanone, ascaridol, carvacrol, isoascaridol, methyl salicylate, p-cymene and/or γ-terpinene, were putatively considered responsible for CRKN hatching inhibition. S. montana and T. capitata OCM fractions showed hatching inhibitions higher than HM fractions. The comparison of EO and corresponding fractions EC50 values suggests interactions between OCM and HM fractions against CRKN hatching. These species EOs showed to be potential environmentally friendly CRKN hatching inhibitors; nonetheless, bioactivity should be considered globally, since its HM and OCM fractions may contribute, diversely, to the full anti-hatching activity.

Novel bio-based amine curing agents for epoxy resins: the way towards fully bio-based composite materials

Epoxy resins are widely used in many applications, such as paints, adhesives and matrices for composites materials, since they present the possibility to be easily and conveniently tailored in order to display a unique combination of characteristics. In literature, various examples of bio-based epoxy resins produced from a wide range of renewable sources can be found. Nevertheless, the toxicity and safety of curing agents have not been deeply investigated and it was observed that all of them still present some environmental drawback. Therefore, the development of new environmentally friendly fully bio-based epoxy systems is of great importance for designing green and sustainable materials. In this context, the present project aims at further exploring the possibility of using bio-based compounds as curing agents for epoxy resin precursors. A preliminary evaluation of several amine-based compounds demonstrated the feasibility of using Adenine as epoxy resin hardener. In order to better understand the crosslinking mechanism, the reaction of Adenine with the mono-epoxy compound Glycidyl 2-methylphenyl ether (G2MPE), was study by 1H-NMR analysis. Then Adenine was investigated as hardener of Diglycidil ether of bisphenol A (DGEBA), which is the simplest epoxy resin based on bisphenol A, in order to determine the best hardener/resin stoichiometric ratio, and evaluate the crosslinking kinetics and conversion and the final mechanical properties of the cured resin. Then, Adenine was tested as hardener of commercial epoxy resins, in particular the infusion resin Elan-tron® EC 157 (Elantas), the impregnation resin EPON™ Resin 828 (Hexion) and the bio-based resin SUPER SAP® CLR (Entropyresins). Such systems were used for the production of composites materials reinforced with chopped recycled carbon fibers and natural fibers (flax and jute). The thermo-mechanical properties of these materials have been studied in comparison with those ones of composites obtained with the same thermosetting resin reinforced with chopped virgin carbon fibers.

Assessing the impact of ammonia content in VFA-rich streams on the PHA-storing MMC acclimatization and the PHA production stage

The use of environmentally friendly products increased the interest in renewable resources as alternatives to petrochemical products. Polyhydroxyalkanoates (PHAs) are examples of such promising products, as they are biodegradable polymers with numerous potential applications. PHA production approach consists of using an open mixed microbial culture (MMC) and inexpensive feedstocks (waste or industry byproducts feedstock). The PHA process generally comprises three stages: (1) acidogenic fermentation (AF) stage (conversion of organic carbon into fermentation products); (2) culture selection stage (enrichment in PHA-storing organisms by applying Feast and Famine regime); and (3) PHA production stage (PHA accumulation up to the culture’s maximum capacity). AF of protein-rich residues results in ammonia-rich fermented streams, which can be presented as a challenge for the PHA production stage. The presence of ammonia during this stage may induce organisms to grow instead of producing PHAs. For this reason, the assessment of the effect of a high content of ammonia on PHA production it is the utmost importance. The main goal of the current project is to select a MMC enriched in PHA-accumulating organisms in conditions of high ammonia content and to evaluate the effects of ammonia presence during PHA accumulation. The culture was selected applying the Feast & Famine strategy, and fed, firstly, using a synthetic mixture of VFAs and later using a fermented stream obtained from the fermentation of protein-rich raw materials. The selected culture could accumulate up to 24% PHA per VSS with the synthetic mixture of VFAs and up to 29% for the real fermented stream. The PHA accumulation resulted in different production in the presence and absence of ammonia. Regarding to the synthetic feed, 59%wt. PHA (VSS basis) in the absence of ammonia, and 55%wt. (VSS basis) in the presence, were obtained. For the real feed, the PHA content was about 40%wt. (VSS basis) in both reactors.

Collective actions for environmental monitoring and conservation: citizen science, informal environmental education, and participatory approach

This PhD was driven by an interest for inclusive and participatory approaches. The methodology that bridges science and society is known as 'citizen science' and is experiencing a huge upsurge worldwide, in the scientific and humanities fields. In this thesis, I have focused on three topics: i) assessing the reliability of data collected by volunteers; ii) evaluating the impact of environmental education activities in tourist facilities; and iii) monitoring marine biodiversity through citizen science. In addition to these topics, during my research stay abroad, I developed a questionnaire to investigate people's perceptions of natural areas to promote the implementation of co-management. The results showed that volunteers are not only able to collect sufficiently reliable data, but that during their participation in this type of project, they can also increase their knowledge of marine biology and ecology and their awareness of the impact of human behaviour on the environment. The short-term analysis has shown that volunteers are able to retain what they have learned. In the long term, knowledge is usually forgotten, but awareness is retained. Increased awareness could lead to a change in behaviour and in this case a more environmentally friendly attitude. This aspect could be of interest for the development of environmental education projects in tourism facilities to reduce the impact of tourism on the environment while adding a valuable service to the tourism offer. We also found that nature experiences in childhood are important to connect to nature in adulthood. The results also suggest that membership or volunteering in an environmental education association could be a predictor of people's interest in more participatory approaches to nature management. In most cases, the COVID -19 pandemic had not changed participants' perceptions of the natural environment.

High friction and acoustic surface for pavements: development of artificial engineered aggregates from recycled powders

There is a constant need to improve the infrastructure's quality and build new infrastructure with better designs. The risk of accidents and noise can be reduced by improving the surface properties of the pavement. The amount of raw material used in road construction is worrisome, as it is finite and due the waste produced. Environmentally-friendly roads construction, recycling might be the main way. Projects must be more environmentally-friendly, safer, and quieter. Is it possible to develop a safer, quieter and environmentally-friendly pavement surfaces? The hypothesis is: is it possible to create an Artificial Engineered Aggregate (AEA) using waste materials and providing it with a specific shape that can help to reduce the noise and increase the friction? The thesis presents the development of an AEA and its application as a partial replacement in microsurfacing samples. The 1st introduces the topic and provides the aim and objectives of the thesis. The 2nd chapter – presents a pavement solution to noise and friction review. The 3rd chapter - developing a mix design for a geopolymer mortar that used basalt powder. The 4th chapter is presented the physical-mechanical evaluation of the AEA. The 5th chapter evaluates the use of this aggregate in microsurfacing regarding the texture parameters. The 6th chapter, those parameter are used as an input to SPERoN® model, simulating their noise behavior of these solutions. The findings from this thesis are presented as partial conclusions in each chapter, to be closed in a final chapter. The main findings are: the DoE provided the tool to select the appropriate geopolymer mortar mix design; AEA had interesting results regarding the physical-mechanical tests; AEA in partial replacement of the natural aggregates in microsurfacing mixture proved feasible. The texture parameters and noise levels obtained in AEA samples demonstrate that it can serve as a HIFASP

Towards cheaper, safer and low environmental impact materials for energy storage devices: natural resources-derived carbon based electrodes and aqueous electrolytes for supercapacitors

The growing market of electrical cars, portable electronics, photovoltaic systems..etc. requires the development of efficient, low-cost, and low environmental impact energy storage devices (ESDs) including batteries and supercapacitors.. Due to their extended charge-discharge cycle, high specific capacitance, and power capabilities supercapacitors are considered among the most attractive ESDs. Over the last decade, research and development in supercapacitor technology have accelerated: thousands of articles have been published in the literature describing the electrochemical properties of the electrode materials and electrolyte in addition to separators and current collectors. Carbon-based supercapacitor electrodes materials have gained increasing attention due to their high specific surface area, good electrical conductivity, and excellent stability in harsh environments, as well as other characteristics. Recently, there has been a surge of interest in activated carbon derived from low-cost abundant sources such as biomass for supercapacitor electrode materials. Also, particular attention was given to a major challenging issue concerning the substitution of organic solutions currently used as electrolytes due to their highest electrochemical stability window even though their high cost, toxicity, and flammability. In this regard, the main objective of this thesis is to investigate the performances of supercapacitors using low cost abundant safe, and low environmental impact materials for electrodes and electrolytes. Several prototypes were constructed and tested using natural resources through optimization of the preparation of appropriate carbon electrodes using agriculture by-products waste or coal (i.e. Argan shell or Anthracite from Jerrada). Such electrodes were tested using several electrolyte formulations (aqueous and water in salt electrolytes) beneficing their non-flammability, lower cost, and environmental impact; the characteristics that provide a promising opportunity to design safer, inexpensive, and environmentally friendly devices compared to organic electrolytes.

Design of mobility infrastructures to promote sustainability and accessibility of urban areas

This doctoral dissertation represents a cluster of research activities carried out at the DICAM Department of the University of Bologna during a three-year Ph.D. course. The goal of this research is to show how the development of an interconnected infrastructure network, aimed at promoting accessibility and sustainability of places, is fundamental in a framework of deep urban regeneration. Sustainable urban mobility plays an important role in improving the quality of life of citizens. From an environmental point of view, a sustainable mobility system means reducing fuel discharges and energy waste and, in general, aims to promote low carbon emissions. At the same time, a socially and economically sustainable mobility system should be accessible to everybody and create more job opportunities through better connectivity and mobility. Environmentally friendly means of transport such as non-motorized transport, electric vehicles, and hybrid vehicles play an important role in achieving sustainability but require a planned approach at the local policy level. The aim of this study is to demonstrate that, through a targeted reconnection of road and cycle-pedestrian routes, the quality of life of an urban area subject to degradation can be significantly improved just by increasing its accessibility and sustainability. Starting from a detailed study of the European policies and from the comparison with real similar cases, the case study of the Canal Port of Rimini (Italy) has been analysed within the European project FRAMESPORT. The analysis allowed the elaboration of a multicriterial methodology to get to the definition of a project proposal and of a priority scale of interventions. The applied methodology is a valuable tool that may be used in the future in similar urban contexts. Finally, the whole project was represented by using virtual reality to visually show the difference between the before and after the regeneration intervention.

Sustainable pavements for rural scenarios: laboratory and in-situ characterization of recycled materials and innovative construction solutions

Growing need for infrastructure has led to expanding research on advances in road pavement materials. Finding solutions that are sustainable, environmentally friendly and cost-efficient is a priority. Focusing such efforts on low-traffic and rural roads can contribute with a significant progress in the vital circulatory system of transport for rural and agricultural areas. An important alternative material for pavement construction is recycled aggregates from solid wastes, including waste from civil engineering activities, mainly construction and demolition. A literature review on studies is made; it is performed a planned set of laboratory testing procedures aimed to fully characterize and assess the potential in-situ mechanical performance and chemical impact. Furthermore, monitoring the full-scale response of the selected materials in a real field construction site, including the production, laying and compaction operations. Moreover, a novel single-phase solution for the construction of semi-flexible paving layers to be used as alternative material to common concrete and bituminous layers is experimented and introduced, aiming the production and laying of a single-phase laid material instead of a traditional two phases grouted macadam. Finally, on a parallel research work for farming pavements, the possible use of common geotechnical anti-erosive products for the improvement of soil bearing capacity of paddock areas in cattle husbandries of bio-farms is evaluated. this thesis has clearly demonstrated the feasibility of using the sustainable recycled aggregates for low-traffic rural roads and the pavements of farming and agriculture areas. The pavement layers constructed with recycled aggregates provided satisfying performance under heavy traffic conditions in experimental pavements. This, together with the fact that these aggregates can be available in most areas and in large quantities, provides great impetus towards shifting from traditional materials to more sustainable alternatives. The chemical and environmental stability of these materials proves their soundness to be utilized in farming environments.

An analysis of the regulatory chill hypothesis: environmental protection in international investment law

The goal of this thesis has been to find out whether ISDS and international investment law exert a chilling effect on more stringent environmental standards at the domestic level. Due to the lack of consistent empirical and statistical evidence uncovered during the analysis, this thesis largely dismisses the regulatory chill hypothesis. However, two exceptions are identified: first, there is evidence of the efforts made by domestic industrial groups and trade unions to prevent the implementation of stricter environmental standards; second, it has become apparent that unfounded beliefs, e.g. about ISDS, held by lawmakers and regulators can play an important role in chilling stricter environmental standards. For these reasons, a new and narrower definition of the regulatory chill phenomenon has been proposed, one that only encompasses those instances in which lawmakers, governments and government agencies refrain from adopting the laws and regulations that they deem the most appropriate because they believe that doing so would lead to adverse consequences at the international trade and investment level, despite a lack of consistent and robust evidence supporting their concerns. The second part of this thesis focusses on what could be done in international economic law to promote environmentally friendly FDI, while preventing the few instances in which regulatory chill may take place due to ill-founded beliefs held by lawmakers and regulators. Following an analysis that highlights the paramount role played by public participation and responsive institutions to achieve an appropriate level of environmental protection, this study ends with a proposal that recommends the adoption of a clause within IIAs that makes pre-investment environmental screening mandatory and free from ISDS oversight.

Nanocomposites based on poly(caprolactone)-chitosan electrospun nanofibers and metallic oxide nanoparticles. Their potential use to adsorption and photocatalytic degradation of organic contaminants

Pollution of water bodies is one of the most common environmental problems today. Organic pollutants are one of the main drawbacks in this natural resource, among which the following stand out long-lived dyes, pharmaceuticals, and pesticides. This research aims at obtaining nanocomposites based on polycaprolactone-chitosan (PCL-CS) electrospun nanofibers (NFs) containing TiO2 nanoparticles (NPs) for the adsorption and photocatalytic degradation of organic pollutants, using Rhodamine B as a model. The fabricated hybrid materials were characterized by FT-IR, TGA, DSC, SEM, TEM, tensile properties, and the contact angle of water drops. The photoactivity of the NFs was investigated using a batch-type system by following UV-Vis absorbance and fluorescence of rhodamine B (RhB). For this purpose, TiO2NPs were successfully ex-situ incorporated into the polymer matrix promoting good mechanical properties and higher hydrophilicity of the material. The results showed that CS in the NFs increased the absorption and degradation of RhB by the TiO2NPs. CS attracted the pollutant molecules to the active sites vicinity of TiO2NPs, favoring initial adsorption and degradation. In other words, a bait-hook-and-destroy effect was evidenced. It also was demonstrated that the sensitization of TiO2 by organic dyes (e.g., perylene derivative) considerably improves the photocatalytic activity under visible radiation, allowing the use of low amounts of TiO2. (≈0.05 g/1 g of fiber). Hence, the current study is expected to contribute with an environmentally friendly green alternative solution.

SmartForge: An event-driven architecture for simulator-based process optimization

In the metal industry, and more specifically in the forging one, scrap material is a crucial issue and reducing it would be an important goal to reach. Not only would this help the companies to be more environmentally friendly and more sustainable, but it also would reduce the use of energy and lower costs. At the same time, the techniques for Industry 4.0 and the advancements in Artificial Intelligence (AI), especially in the field of Deep Reinforcement Learning (DRL), may have an important role in helping to achieve this objective. This document presents the thesis work, a contribution to the SmartForge project, that was performed during a semester abroad at Karlstad University (Sweden). This project aims at solving the aforementioned problem with a business case of the company Bharat Forge Kilsta, located in Karlskoga (Sweden). The thesis work includes the design and later development of an event-driven architecture with microservices, to support the processing of data coming from sensors set up in the company's industrial plant, and eventually the implementation of an algorithm with DRL techniques to control the electrical power to use in it.

Niobium-based heterogeneous catalysts synthesised in supercritical carbon dioxide for selective olefin epoxidation

In this work, two different protocols for the synthesis of Nb2O5-SiO2 with a sol-gel route in which supercritical carbon dioxide was used as solvent have been developed. The tailored design of the reactor allowed the reactants to come into contact only when supercritical CO2 is present, and the high-throughput experimentation scCO2 unit allowed the screening of synthetic parameters, that led to a Nb2O5 incorporation into the silica matrix of 2.5 wt%. N2-physisorption revealed high surface areas and the presence of meso- and micropores. XRD allowed to demonstrate the amorphous character of these materials. SEM-EDX proved the excellent dispersion of Nb2O5 into the silica matrix. These materials were tested in the epoxidation of cyclooctene with hydrogen peroxide, which is considered an environmentally friendly oxidant. The catalysts were virtually inactive in an organic, polar, aprotic solvent (1,4-dioxane). However, the most active scCO2 Nb2O5-SiO2 catalyst achieved a cyclooctene conversion of 44% with a selectivity of 88% towards the epoxide when tested in ethanol. Catalytic tests on cyclohexene revealed the presence of the epoxide, which is remarkable, considering that this substrate is easily oxidised to the diol. The behaviour in protic and aprotic solvents is compared to that of TS-1.

Spatial Technologies: What use are they to managers of environmental lands?

This paper reviews the potential use of three types of spatial technology to land managers, namely satellite imagery, satellite positioning systems and supporting computer software. Developments in remote sensing and the relative advantages of multispectral and hyperspectral images are discussed. The main challenge to the wider use of remote sensing as a land management tool is seen as uncertainty whether apparent relationships between biophysical variables and spectral reflectance are direct and causal, or artefacts of particular images. Developments in satellite positioning systems are presented in the context of land managers’ need for position estimates in situations where absolute precision may or may not be required. The role of computer software in supporting developments in spatial technology is described. Spatial technologies are seen as having matured beyond empirical applications to the stage where they are useful and reliable land management tools. In addition, computer software has become more user-friendly and this has facilitated data collection and manipulation by semi-expert as well as specialist staff.