Swelling properties of alkali-metal doped polymeric anion-exchange membranes in alcohol media for application in fuel cells

Swelling properties of four commercial anion-exchange membranes with different structure have been analyzed in several hydro-organic media. With this target, the liquid uptake and the surface expansion of the membranes in contact with different pure liquids, water and alcohols (methanol, ethanol and 1-propanol), and with water alcohol mixtures with different concentrations have been experimentally determined in presence and in absence of an alkaline medium (LiOH, NaOH and KOH of different concentrations). The alkali-metal doping effect on the membrane water uptake has also been investigated, analyzing the influence of the hydroxide concentration and the presence of an alcohol in the doping solution. The results show that the membrane structure plays an essential role in the influence that alcohol nature and alkaline media has on the selective properties of the membrane. The heterogeneous membranes, with lower density, show higher liquid uptakes and dimensional changes than the homogeneous membranes, regardless of the doping conditions. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Influence of the metal center on the morphology of coordination compounds thin films

Thin film morphology of tris-(8-hydroxyquinolate) aluminium (III) (Alq3) and bis-(8-hydroxyquinolate) oxovanadium (IV) (VOq2) are compared. Alq3 films deposited onto mica at 300K look almost featureless, but dendrimers or randomly distributed needle-shaped crystallites appear as a consequence of crystallization in time. We show that a possible origin of this process is exposure to solvent vapors. On the other hand, VOq2 films retain their textured morphology as thickness increases because of stabilizing intermolecular interactions between vanadyl groups.

Towards near-infrared photoactivation of anticancer metal complexes.

171 p.

Influence of the metal precursor on the catalytic behavior of Pt/Ceria catalysts in the preferential oxidation of CO in the presence of H2 (PROX)

The effect of the metal precursor (presence or absence of chlorine) on the preferential oxidation of CO in the presence of H2 over Pt/CeO2 catalysts has been studied. The catalysts are prepared using (Pt(NH3)4)(NO3)2 and H2PtCl6, as precursors, in order to ascertain the effect of the chlorine species on the chemical properties of the support and on the catalytic behavior of these systems in the PROX reaction. The results show that chloride species exert an important effect on the redox properties of the oxide support due to surface chlorination. Consequently, the chlorinated catalyst exhibits a poorer catalytic activity at low temperatures compared with the chlorine-free catalyst, and this is accompanied by a higher selectivity to CO2 even at high reaction temperatures. It is proposed that the CO oxidation mechanism follows different pathways on each catalyst.

Influence of the metal center on the morphology of coordination compounds thin films

Thin film morphology of tris-(8-hydroxyquinolate) aluminium (III) (Alq3) and bis-(8-hydroxyquinolate) oxovanadium (IV) (VOq2) are compared. Alq3 films deposited onto mica at 300K look almost featureless, but dendrimers or randomly distributed needle-shaped crystallites appear as a consequence of crystallization in time. We show that a possible origin of this process is exposure to solvent vapors. On the other hand, VOq2 films retain their textured morphology as thickness increases because of stabilizing intermolecular interactions between vanadyl groups.

CO-ELECTROPHORETIC DEPOSITION OF LIQUID METAL AND SILICON FOR LITHIUM-ION BATTERY APPLICATION

A low cost electrophoretic deposition (EPD) process was successfully used for liquid metal thin film deposition with a high depositing rate of 0.6 µ/min. Furthermore, silicon nano-powder and liquid metal were then simultaneously deposited as the negative electrode of lithium-ion battery by a technology called co-EPD. The liquid metal was hoping to act as the matrix for silicon particles during lithium ion insertion and distraction. Half-cell testing was performed using as prepared co-EPD sample. An initial discharge capacity of 1500 mAh/g was reported for nano-silicon and galinstan electrode, although the capacity fading issue of these samples was also observed.

Design, development, and analysis of hybrid metal-composite tube for industrial application

In the aerospace, automotive, printing, and sports industries, the development of hybrid Carbon Fiber Reinforced Polymer (CFRP)-metal components is becoming increasingly important. The coupling of metal with CFRP in axial symmetric components results in reduced production costs and increased mechanical properties such as bending, torsional stiffness, mass reduction, damping, and critical speed compared to the single material-built ones. In this thesis, thanks to a novel methodology involving a rubbery/viscoelastic interface layer, several hybrid aluminum-CFRP prototype tubes were produced. Besides, an innovative system for the cure of the CFRP part has been studied, analyzed, tested, and developed in the company that financed these research activities (Reglass SRL, Minerbio BO, Italy). The residual thermal stresses and strains have been investigated with numerical models based on the Finite Element Method (FEM) and compared with experimental tests. Thanks to numerical models, it was also possible to reduce residual thermal stresses by optimizing the lamination sequence of CFRP and determining the influence of the system parameters. A novel software and methodology for evaluating mechanical and damping properties of specimens and tubes made in CFRP were also developed. Moreover, to increase the component's damping properties, rubber nanofibers have been produced and interposed throughout the lamination of specimens. The promising results indicated that the nanofibrous mat could improve the material damping factor over 77% and be adopted in CFRP components with a negligible increment of weight or losing mechanical properties.

Synthesis and Characterization of Double Metal Hexacyanoferrates

Manganese Hexacyanoferrate (MnHCF) and nickel doped manganese hexacyanoferrate were synthesized by simple co-precipitation method. The water content and chemical formula was obtained by TGA and MP-AES measurements, functional groups by FT-IR analysis, the crystal structure by PXRD and a local geometry by XAS. Elemental species of cycled samples were further investigated by TXM and 2D XRF. Electrochemical tests were performed in the glass cell. With addition of nickel, vacancies and water content increased in the sample. Crystal structure changed from monoclinic to cubic. Ni disturbed the local structure of Mn, site, however, almost no change was observed in Fe site. After charge/discharge cycling of MnHCF intercalation was already found in the peripheries of charged species after 20 cycle in 2D XRF analysis and randomly distributed intercalated regions after 50 cycles in TXM analysis. Cyclic voltammetry showed that peak-to-peak separation is increasing in case of the addition of Ni to MnHCF.

Development of a numerical platform for the modeling and optimal control of liquid metal flows

The main purpose of this work is to develop a numerical platform for the turbulence modeling and optimal control of liquid metal flows. Thanks to their interesting thermal properties, liquid metals are widely studied as coolants for heat transfer applications in the nuclear context. However, due to their low Prandtl numbers, the standard turbulence models commonly used for coolants as air or water are inadequate. Advanced turbulence models able to capture the anisotropy in the flow and heat transfer are then necessary. In this thesis, a new anisotropic four-parameter turbulence model is presented and validated. The proposed model is based on explicit algebraic models and solves four additional transport equations for dynamical and thermal turbulent variables. For the validation of the model, several flow configurations are considered for different Reynolds and Prandtl numbers, namely fully developed flows in a plane channel and cylindrical pipe, and forced and mixed convection in a backward-facing step geometry. Since buoyancy effects cannot be neglected in liquid metals-cooled fast reactors, the second aim of this work is to provide mathematical and numerical tools for the simulation and optimization of liquid metals in mixed and natural convection. Optimal control problems for turbulent buoyant flows are studied and analyzed with the Lagrange multipliers method. Numerical algorithms for optimal control problems are integrated into the numerical platform and several simulations are performed to show the robustness, consistency, and feasibility of the method.

Impacts of trace element pollution on sewage sludge and soil-plant systems: developing remediation techniques and assessing plant uptake prevention measures

Trace Elements (TEs) pollution is a significant environmental concern due to its toxic effects on human and ecosystem health and its potential to bioaccumulate in the food chain and to threaten species survival, leading to a decline in biodiversity. Urban areas, industrial and mining activities, agricultural practices, all contribute to the release of TEs into the environment posing a significant risk to human health and ecosystems. Several techniques have been developed to control TEs into the environment. This work presents the findings of three-year PhD program that focused on research on TEs pollution. The study discusses three fundamental aspects related to this topic from the perspective of sustainable development, environmental and human health. (1) High levels of TEs contamination prevent the use of sewage sludge (SS) as a fertilizer in agriculture, despite its potential as a soil amendment. Developing effective techniques to manage TEs contamination in SS is critical to ensure its safe use in agriculture and promote resource efficiency through sludge reuse. Another purpose of the study was to evaluate different strategies to limit the TEs uptake by horticultural crops (specifically, Cucumis Melo L.). This study addressed the effect of seasonality, Trichoderma inoculation and clinoptilolite application on chromium (Cr), copper (Cu) and lead (Pb) content of early- and late-ripening cultivars of Cucumis Melo L.. Finally, the accumulation of copper and the effect of its bioavailable fraction on bacterial and fungal communities in the rhizosphere soil of two vineyards, featuring two different varieties of Vitis vinifera grown for varying lengths of time, were evaluated.

Synthesis, characterization and potential applications of novel metal-organic frameworks

​The research work described in this thesis concerns the synthesis, characterization, and applications of two kinds of metal-organic frameworks (MOFs), Copper based MOF (Cu-MOF) and zirconium based MOF (Zr-MOF) functionalized with new linkers. ​The common thread of this research project can be summarized in three work phases: ​first, the synthesis and characterization of new organic linkers is described, followed by the presentation of the different optimization conditions for the MOFs synthesis. ​Second, the new materials were fully characterized using several complementary techniques, such as infrared (ATR-FTIR) and Raman spectroscopy, X-ray powder diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS) as well as thermal and surface area measurements. ​Final, to obtain a complete work the possible environmental applications of the new materials were explored.

Design of luminescent metal complexes for polymer science

The program of my PhD studies has been dealing with the investigation of the research outcomes that may result from the use of luminescent Iridium(III) cyclometalated complexes in the field of polymer science. In particular, my activity has been focused on exploring two main applicative contexts, i.e. Ir(III) complexes for preparing polymers and in combination with polymers. In the first part, a new set of luminescent Ir(III) complexes was exploited as photocatalysts for light-assisted atom transfer radical polymerization of methyl methacrylate. The decoration of both cyclometalated and ancillary ligands with sp3 hybridized nitrogen substituents together with the use of specific counterions, imparted suitable photophysical and redox properties for an efficient photocatalyzed process. The second part has been focused on the employment of Ir(III) tetrazole complexes as phosphorescent dyes in polymeric materials. Colourless luminescent solar concentrators were prepared blending two Ir(III) cyclometalates with acrylate polymers. Their performances were investigated, leading to promising outcomes comparable, or superior, to those obtained from colourless LSCs based on organic fluorophores. As a complementary approach, Ir(III) complexes were covalently linked to polymers in the side chain, to obtain a new class of metallopolymers. To this extent, a bifunctional tetrazolate molecule, equipped with a coordination site and a polymerizable unit, was designed. The photophysical properties of the resultant luminescent polymeric films were discussed. In the end, an additional project involving both polymers and metal compounds was carried out during my experience as a visiting PhD student at Humboldt – University of Berlin. Polystyrene and polyethylene glycol -based ion-exchange resins were functionalized with peptides through a ligation pathway, for the selective chelation of Copper(II) in aqueous solutions. The coordinating capability of the materials towards Cu2+ ions was tested by ICP-MS analysis. The resins strategically modified with ion-selective peptides, may be exploited in the preparation of water-processing devices.

Excitonic properties of transition metal oxide perovskites and workflow automatization of GW schemes

The Many-Body-Perturbation Theory approach is among the most successful theoretical frameworks for the study of excited state properties. It allows to describe the excitonic interactions, which play a fundamental role in the optical response of insulators and semiconductors. The first part of the thesis focuses on the study of the quasiparticle, optical and excitonic properties of \textit{bulk} Transition Metal Oxide (TMO) perovskites using a G$_0$W$_0$+Bethe Salpeter Equation (BSE) approach. A representative set of 14 compounds has been selected, including 3d, 4d and 5d perovskites. An approximation of the BSE scheme, based on an analytic diagonal expression for the inverse dielectric function, is used to compute the exciton binding energies and is carefully bench-marked against the standard BSE results. In 2019 an important breakthrough has been achieved with the synthesis of ultrathin SrTiO3 films down to the monolayer limit. This allows us to explore how the quasiparticle and optical properties of SrTiO3 evolve from the bulk to the two-dimensional limit. The electronic structure is computed with G0W0 approach: we prove that the inclusion of the off-diagonal self-energy terms is required to avoid non-physical band dispersions. The excitonic properties are investigated beyond the optical limit at finite momenta. Lastly a study of the under pressure optical response of the topological nodal line semimetal ZrSiS is presented, in conjunction with the experimental results from the group of Prof. Dr. Kuntscher of the Augsburg University. The second part of the thesis discusses the implementation of a workflow to automate G$_0$W$_0$ and BSE calculations with the VASP software. The workflow adopts a convergence scheme based on an explicit basis-extrapolation approach [J. Klimeš \textit{et al.}, Phys. Rev.B 90, 075125 (2014)] which allows to reduce the number of intermediate calculations required to reach convergence and to explicit estimate the error associated to the basis-set truncation.

Inhibition and characterization of two-metal ion enzymes to treat cancer: dna polymerase Ƞ and topoisomerase II α

Chemotherapeutic drugs can in many ways disrupt the replication machinery triggering apoptosis in cancer cells: some act directly on DNA and others block the enzymes involved in preparing DNA for replication. Cisplatin-based drugs are common as first-line cancer chemotherapics. Another example is etoposide, a molecule that blocks topoisomerase II α leading to the inhibition of dsDNA replication. Despite their efficacy, cancer cells can respond to these treatments over time by overtaking their effects, leading to drug resistance. Chemoresistance events can be triggered by the action of enzymes like DNA polymerase ƞ (Pol η). This polymerase helps also to bypass drug-induced damage in cancer cells, allowing DNA replication and cancer cells proliferation even when cisplatin-based chemotherapeutic drugs are in use. Pol ƞ is a promising drug discovery target, whose inhibition would help in overcoming of drug resistance. This study aims to identify a potent and selective Pol ƞ inhibitor able to improve the efficacy of platinum-based chemotherapeutic drugs. We report the discovery of compound 64 (ARN24964), after an extensive SAR reporting 35 analogs. We evaluated compound 64 on four different cell lines. Interestingly, the molecule is a Pol η inhibitor able to act synergistically with cisplatin. Moreover, we also synthesized a prodrug form that allowed us to improve its stability and the bioavailability. This compound represents an advanced scaffold featuring good potency and DMPK properties. In addition to this central theme, this thesis also describes our efforts in developing and characterize a novel hybrid inhibitor/poison for the human topoisomerase II α enzyme. In particular, we performed specific assays to study the inhibiton of Topoisomesare II α and we evaluated compounds effect on three cancer cell lines. These studies allowed us to identify a compound that is able to inhibit the enzyme with a good pK and a good potency.