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.

An eco-friendly way to fire retardant flexible polyurethane foam: layer-by-layer assembly of fully bio-based substances

The objective of the present study is to develop fully renewable and environmentally benign techniques for improving the fire safety of flexible polyurethane foams (PUFs). A multilayered coating made from cationic chitosan (CS) and anionic alginate (AL) was deposited on PUFs through layer-by-layer assembly. This coating system exhibits a slight influence on the thermal stability of PUF, but significantly improves the char formation during combustion. Cone calorimetry reveals that 10 CS-AL bilayers (only 5.7% of the foams weight) lead to a 66% and 11% reduction in peak heat release rate and total heat release, respectively, compared with those of the uncoated control. The notable decreased fire hazards of PUF are attributed to the CS-AL coatings being beneficial to form an insulating protective layer on the surface of burning materials that inhibits the oxygen and heat permeation and slows down the flammable gases in the vapor phase, and thereby improves the flame resistance. This water-based, environmentally benign natural coating will stimulate further efforts in improving fire safety for a variety of polymer substrates.

Sim-xl: A Powerful And User-friendly Tool For Peptide Cross-linking Analysis.

Chemical cross-linking has emerged as a powerful approach for the structural characterization of proteins and protein complexes. However, the correct identification of covalently linked (cross-linked or XL) peptides analyzed by tandem mass spectrometry is still an open challenge. Here we present SIM-XL, a software tool that can analyze data generated through commonly used cross-linkers (e.g., BS3/DSS). Our software introduces a new paradigm for search-space reduction, which ultimately accounts for its increase in speed and sensitivity. Moreover, our search engine is the first to capitalize on reporter ions for selecting tandem mass spectra derived from cross-linked peptides. It also makes available a 2D interaction map and a spectrum-annotation tool unmatched by any of its kind. We show SIM-XL to be more sensitive and faster than a competing tool when analyzing a data set obtained from the human HSP90. The software is freely available for academic use at http://patternlabforproteomics.org/sim-xl. A video demonstrating the tool is available at http://patternlabforproteomics.org/sim-xl/video. SIM-XL is the first tool to support XL data in the mzIdentML format; all data are thus available from the ProteomeXchange consortium (identifier PXD001677).

To Monty Kier, a friendly tribute.

In 2008 we published the first set of guidelines for standardizing research in autophagy. Since then, research on this topic has continued to accelerate, and many new scientists have entered the field. Our knowledge base and relevant new technologies have also been expanding. Accordingly, it is important to update these guidelines for monitoring autophagy in different organisms. Various reviews have described the range of assays that have been used for this purpose. Nevertheless, there continues to be confusion regarding acceptable methods to measure autophagy, especially in multicellular eukaryotes. A key point that needs to be emphasized is that there is a difference between measurements that monitor the numbers or volume of autophagic elements (e.g., autophagosomes or autolysosomes) at any stage of the autophagic process vs. those that measure flux through the autophagy pathway (i.e., the complete process); thus, a block in macroautophagy that results in autophagosome accumulation needs to be differentiated from stimuli that result in increased autophagic activity, defined as increased autophagy induction coupled with increased delivery to, and degradation within, lysosomes (in most higher eukaryotes and some protists such as Dictyostelium) or the vacuole (in plants and fungi). In other words, it is especially important that investigators new to the field understand that the appearance of more autophagosomes does not necessarily equate with more autophagy. In fact, in many cases, autophagosomes accumulate because of a block in trafficking to lysosomes without a concomitant change in autophagosome biogenesis, whereas an increase in autolysosomes may reflect a reduction in degradative activity. Here, we present a set of guidelines for the selection and interpretation of methods for use by investigators who aim to examine macroautophagy and related processes, as well as for reviewers who need to provide realistic and reasonable critiques of papers that are focused on these processes. These guidelines are not meant to be a formulaic set of rules, because the appropriate assays depend in part on the question being asked and the system being used. In addition, we emphasize that no individual assay is guaranteed to be the most appropriate one in every situation, and we strongly recommend the use of multiple assays to monitor autophagy. In these guidelines, we consider these various methods of assessing autophagy and what information can, or cannot, be obtained from them. Finally, by discussing the merits and limits of particular autophagy assays, we hope to encourage technical innovation in the field.

The effect of environmentally differentiated port fees to shipping companies’ environmental investments

The pressure has grown to develop cost-effective emission reduction strategies in the Baltic Sea. The forthcoming stringent regulations of the International Maritime Organization for reducing harmful emissions of shipping in the Baltic Sea are causing increasing expenses for the operators. A market-based attitude towards pricing of economic incentives could be seen as a new approach for a successful application for the additional emission reduction of nitrogen oxides (NOx). In this study the aim is to understand the phenomenon of environmentally differentiated port fees and its effects on shipping companies’ emission reduction investments. The goal is to examine empirically the real-life effects of the possible environmental differentiated port fee system and the effect of environmentally differentiated port fees on NOx reduction investments in the Baltic Sea. The research approach of this study is nomothetical. In this study research questions are answered by analyzing the broad database of the Baltic Sea fleet. Also the framework of theory is confirmed and plays an important role in analyzing the research problem. Existing investment costs of NOx emission reduction technology to ship owners are estimated and compared to investment costs with granted discounts added to the cash flows. The statistical analysis in this study is descriptive. The major statistic examination of this study is the calculation of the net present values of investments with different port fee scenarios. This is done to investigate if the NOx technology investments could be economically reasonable. Based on calculations it is clear that the effect of environmentally differentiated port fees is not adequate to compensate the total investment costs for NOx reduction. If the investment decision is made only with profitability considerations, sources will prefer to emission abatement as long as incomes from the given subsidy exceeds their abatement costs. Despite of the results, evidence was found that shipping companies are nevertheless willing to invest on voluntary emission abatement technology. In that case, investment decision could be made with criteria of, for example, sustainable strategy or brand image. Combined fairway and port fee system or governmental regulations and recommendation could also function as additional incentives to compensate the investment costs. Also, the results imply that the use of NPV is not necessarily the best method to evaluate environmental investments. If the calculations would be done with more environmental methods the results would probably be different.

Is the OECD acute worm toxicity test environmentally relevant? The effect of mineral form on calculated lead toxicity

In a series of experiments the toxicity of lead to worms in soil was determined following the draft OECD earthworm reproduction toxicity protocol except that lead was added as solid lead nitrate, carbonate and sulphide rather than as lead nitrate solution as would normally be the case. The compounds were added to the test soil to give lead concentrations of 625-12500 pg Pb g-1 of soil. Calculated toxicities of the lead decreased in the order nitrate > carbonate > sulphide, the same order as the decrease in the solubility of the metal compounds used. The 7-day LC50 (lethal concentration when 50% of the population is killed) for the nitrate was 5321 +/- 275 mug Pb g(-1) of soil and this did not change with time. The LC50 values for carbonate and sulphide could not be determined at the concentration ranges used. The only parameter sensitive enough to distinguish the toxicities of the three compounds was cocoon (egg) production. The EC50S for cocoon production (the concentration to produce a 50% reduction in cocoon production) were 993, 8604 and 10 246 mug Pb g(-1) of soil for lead nitrate, carbonate and sulphide, respectively. Standard toxicity tests need to take into account the form in which the contaminant is present in the soil to be of environmental relevance. (C) 2002 Elsevier Science Ltd. All rights reserved.

Electrochemical and sonoelectrochemical monitoring of indigo reduction by glucose

The reduction of indigo (dispersed in water) to leuco-indigo (dissolved in water) is an important industrial process and investigated here for the case of glucose as an environmentally benign reducing agent. In order to quantitatively follow the formation of leuco-indigo two approaches based on (i) rotating disk voltammetry and (ii) sonovoltammetry are developed. Leuco-indigo, once formed in alkaline solution, is readily monitored at a glassy carbon electrode in the mass transport limit employing hydrodynamic voltammetry. The presence of power ultrasound further improves the leuco-indigo determination due to additional agitation and homogenization effects. While inactive at room temperature, glucose readily reduces indigo in alkaline media at 65 degrees C. In the presence of excess glucose, a surface dissolution kinetics limited process is proposed following the rate law d eta(leuco-indigo)/dt = k x c(OH-) x S-indigo where eta(leuco-indigo) is the amount of leuco-indigo formed, k = 4.1 x 10(-9) m s(-1) (at 65 degrees C, assuming spherical particles of I gm diameter) is the heterogeneous dissolution rate constant,c(OH-) is the concentration of hydroxide, and Sindigo is the reactive surface area. The activation energy for this process in aqueous 0.2 M NaOH is E-A = 64 U mol(-1) consistent with a considerable temperature effects. The redox mediator 1,8-dihydroxyanthraquinone is shown to significantly enhance the reaction rate by catalysing the electron transfer between glucose and solid indigo particles. (c) 2006 Elsevier Ltd. All fights reserved.

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - A possible process of the mercury cycle in Brazil

The evolution of elemental Hg from its environmental compounds has already been supposed to be an important process within the global mercury cycle. The present study characterizes the abiotic reduction of Hg(II) ions by typical river humic substances (HS) conventionally pre-isolated by the adsorbent XAD 8 from the Rio Negro near Manaus, Brazil. For the investigation of this reduction process a special reaction and Hg(0) trapping unit combined with cold-vapor atomic absorption spectrometry (CVAAS) was developed. Preconcentration of traces of mercury(II), if required, was obtained by a home-made FIA system using microcolumns filled with the Hg(II)-selective collector CheliteS(R) (Serva Company). The effect of environmentally relevant parameters such as the pH value, the Hg(II)/HS ratio and the HS concentration on the I-IE;(II) reduction process was studied as a function of the time. The Hg(0) production was highest at pH 8.0 and in the case of decreasing HS amounts (0.5 mg) when about 65% of initially 1.0 mug Hg(H) was reduced within 50 h. Moreover, the reduction efficiency of HS towards HE;(II) strongly depended on the HS concentration but hardly on the Hg(II)/HS ratio. The reduction kinetics followed a relatively slow two-step first-order mechanism with formal rate constants of about 0.1 and 0.02 h(-1), respectively. Based on these findings the possible relevance of the abiotic evolution of mercury in humic-rich aquatic environments is considered. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Millennium development goals: advances in environmentally sustainable development in Latin America and the Caribbean

Includes bibliography