Synthesis of novel cobalt and iron complexes for sustainable catalytic hydrogenations

Aim of the present work of thesis is to synthesize new non-noble metal based complexes to be employ in redox reactions by a metal-ligand cooperative mechanism. The need of replacing toxic and expensive precious metal complexes with more available and benign metals, has led to the development of new compounds based on cobalt and iron, which are the metals investigated in this study. A carbonyl-tetrahydroborato-bis[(2-diisopropylphosphino)ethyl]amine-cobalt complex bearing a PNP-type ligand is synthesized by a three-step route. Optimization attempt of reaction route were assessed in order to lowering reaction times and solvent waste. New cobalt complex has been tested in esters hydrogenation as well as in acceptorless dehydrogenative coupling of ethanol. Other varieties of substrates were also tested in order to evaluate any possible applications. Concerning iron complex, dicarbonyl-(η4-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)(1,3-dimethyl-ilidene)iron is synthesized by a three steps route, involving transmetallation of a silver complex, derived from an imidazolium salt, to iron complex. In order to avoid solvent waste, optimization is assessed. Studies were performed to assess activity of triscarbonyl iron precursor toward imidazolium salt and silver complexes.

Study of Co-based hydrotalcite-derived mixed metal oxides partially modified with silver as potential catalysts for N2O decomposition

Co-Al-Ox mixed metal oxides partially modified with Cu or Mg, as well as Ag were successfully prepared, characterized and evaluated as potential catalysts for the N2O decomposition. The materials were characterized by the following techniques: X-Ray Diffraction, Thermogravimetric Analysis (TGA), N2 Physisorption, Hydrogen Temperature-Programmed Reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS). Ag-modified HT-derived mixed oxides showed enhanced activity compared to the undoped materials, the optimum composition was found for (1 wt.% Ag)CHT-Co3Al. The catalyst characterization studies suggested that the improved catalytic activity of Ag-promoted catalysts were mainly because of the altered redox properties of the materials.

Laser shock peening treatment to control and moderate fatigue crack growth in aircraft structure based on residual stress engineering approach

Laser Shock Peening (LSP) is a surface enhancement treatment which induces a significant layer of beneficial compressive residual stresses of up to several mm underneath the surface of metal components in order to improve the detrimental effects of the crack growth behavior rate in it. The aim of this thesis is to predict the crack growth behavior in metallic specimens with one or more stripes which define the compressive residual stress area induced by the Laser Shock Peening treatment. The process was applied as crack retardation stripes perpendicular to the crack propagation direction with the object of slowing down the crack when approaching the peened stripes. The finite element method has been applied to simulate the redistribution of stresses in a cracked model when it is subjected to a tension load and to a compressive residual stress field, and to evaluate the Stress Intensity Factor (SIF) in this condition. Finally, the Afgrow software is used to predict the crack growth behavior of the component following the Laser Shock Peening treatment and to detect the improvement in the fatigue life comparing it to the baseline specimen. An educational internship at the “Research & Technologies Germany – Hamburg” department of AIRBUS helped to achieve knowledge and experience to write this thesis. The main tasks of the thesis are the following: •To up to date Literature Survey related to “Laser Shock Peening in Metallic Structures” •To validate the FE model developed against experimental measurements at coupon level •To develop design of crack growth slowdown in Centered Cracked Tension specimens based on residual stress engineering approach using laser peened strip transversal to the crack path •To evaluate the Stress Intensity Factor values for Centered Cracked Tension specimens after the Laser Shock Peening treatment via Finite Element Analysis •To predict the crack growth behavior in Centered Cracked Tension specimens using as input the SIF values evaluated with the FE simulations •To validate the results by means of experimental tests

Synthesis, characterization and catalytic performances of ruthenium-based catalysts for the acceptorless dehydrogenative coupling of butanol

A growing interest towards new sources of energy has led in recent years to the development of a new generation of catalysts for alcohol dehydrogenative coupling (ADC). This green, atom-efficient reaction is capable of turning alcohol derivatives into higher value and chemically more attractive ester molecules, and it finds interesting applications in the transformation of the large variety of products deriving from biomass. In the present work, a new series of ruthenium-PNP pincer complexes are investigated for the transformation of 1-butanol, one of the most challenging substrates for this type of reactions, into butyl butyrate, a short-chain symmetrical ester widely used in flavor industries. Since the reaction kinetics depends on hydrogen diffusion, the study aimed at identifying proper reactor type and right catalyst concentration to avoid mass transfer interferences and to get dependable data. A comparison between catalytic activities and productivities has been made to establish the role of the different ligands bonded both to the PNP binder and to the ruthenium metal center, and hence to find the best catalyst for this type of reaction.

Late Transition Metal-Oxo complexes: Synthesis, and Biorelevant Reactivity

High-valent terminal metal-oxygen adducts are supposed to be potent oxidising intermediates in enzymatic catalyses. In contrast to those from groups 6-8, oxidants that contain late transition metals (Co, Ni, Cu) are poorly understood. Because of their high reactivity, only a few examples of these compounds have been observed. The aim of this project was to investigate the reactivity of high-valent Ni(III) complexes, containing a monodentate oxygen-donor ligands, in hydrogen atom abstraction (HAA) and oxygen atom transfer (OAT) reactions which are typical of biological high-valent metal-oxygen species. Particularly, the Ni(III) complexes were generated in situ, at low temperature, from the oxidation of the Ni(II) species.The nickel complexes studied during this work were supported by tridentate ligands, with a strong σ-donating ability and exceedingly resistant to several common degradation pathways. These complexes vary based on the monodentate group in the fourth coordination position site, which can be neutral or anionic. In particular, we prepared four different Ni(III) complexes [NiIII(pyN2Me2)(OCO2H)] (12), [NiIII(pyN2Me2)(ONO2)] (14), [NiIII(pyN2Me2)(OC(O)CH3)] (18) and [NiIII(pyN2Me2)(OC(O)H)] (25). They feature a bicarbonate (-OCO2H), nitrate (-ONO2), acetate (-OC(O)CH3) and formate (-OC(O)H) group, respectively.HAA and OAT reactions were performed by adding 2,6-di-tert-butylphenol (2,6-DTBP) at -40°C, and triphenylphosphine (PPh3) at -80°C, to the in situ generated Ni(III) complexes, respectively. These reactions were carried out by adding 7 to 500 equivalents of substrate, in order to ensure pseudo-first order conditions. Since, the reactivity of the Ni(III) complex featured by the bicarbonate group has been studied in a previous work, we only investigated that of the species bearing the nitrate, acetate and formate ligand. Finally we compared the value of the reaction rate of all the four species in the HAA and OAT reactions.

Design and implementation of a non-destructive defect detection technique based on UWB-SAR imaging

In the last twenty years aerospace and automotive industries started working widely with composite materials, which are not easy to test using classic Non-Destructive Inspection (NDI) techniques. Pairwise, the development of safety regulations sets higher and higher standards for the qualification and certification of those materials. In this thesis a new concept of a Non-Destructive defect detection technique is proposed, based on Ultrawide-Band (UWB) Synthetic Aperture Radar (SAR) imaging. Similar SAR methods are yet applied either in minefield [22] and head stroke [14] detection. Moreover feasibility studies have already demonstrated the validity of defect detection by means of UWB radars [12, 13]. The system was designed using a cheap commercial off-the-shelf radar device by Novelda and several tests of the developed system have been performed both on metallic specimen (aluminum plate) and on composite coupon (carbon fiber). The obtained results confirm the feasibility of the method and highlight the good performance of the developed system considered the radar resolution. In particular, the system is capable of discerning healthy coupons from damaged ones, and correctly reconstruct the reflectivity image of the tested defects, namely a 8 x 8 mm square bulge and a 5 mm drilled holes on metal specimen and a 5 mm drilled hole on composite coupon.

Investigation of gold-based catalysts for liquid phase oxidation of glucose to glucaric acid

Glucaric acid (GA) is one of the building block chemicals derived from sugar biomass with higher added value. Nowadays, GA is produced by oxidation of glucose (Glu) with either stoichiometric oxidants (HNO3), or by means of electrochemical or biochemical synthesis. However, these processes show drawbacks from either the environmental or economic viewpoint. For this reason, gold nanoparticles (Au NPs) supported on activated carbon (AC) have been studied as catalysts for the oxidation of Glu, using O2 as oxidant in the presence of a base. Using sol immobilization technique, Au NPs have been supported on AC following different experimental procedures. UV-Vis spectroscopy, XRD, TEM and TG analysis were utilized in the characterization of the catalysts. The operational conditions were optimized obtaining 24% of yield of GA, 37% to GO and 27% to byproducts in 1 h, 1000 rpm, 10 bar of O2 and Glu:Au:NaOH molar ratio of 1000:1:3000. Under such conditions, catalysts show relatively high Glu conversion (≥82%) with different GA yields. GO+GA yield is around 58-61%. Therefore, the oxidation reaction was performed at 15 min where Au/AC PVA0 reached the highest yield of GA (16%) and Au/AC PVA2.4 gave the lowest (8%). It is evident that the presence of PVA influences to a higher degree the reaction rate than the Au NPs size. Hence, the effect of different heat treatments where applied for the removal of PVA: washing with water at 60℃ or heat treatment (120-250℃) with Air/H2. Washing treatment and heat treatment at 120℃ with Air/H2 may have resulted in the mildest treatments for the removal of PVA. Finally, two different supports have been used in order to study the effect of metal-support interaction in the immobilization of Au NPs: ZrO2 and AC. Au/AC catalyst demonstrated a higher conversion of GO to GA at short reaction times (15.1% yield GA) compared to Au/ZrO2 (2.4% yield GA).

Synthesis, Characterization, and Applications of a Novel Cu(II)-MOF Based on a Propargylcarbamate-Functionalized Isophthalate Ligand

This work describes the synthesis of a propargylcarbamate-functionalized isophthalate ligand and its use in the solvothermal preparation of a new copper(II)-based metal organic framework named [Cu(1,3-YBDC)]ˑxH2O (also abbreviated as Cu-MOF. The characterization of this compound was performed 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. Synchrotron X-ray diffraction analysis revealed that this MOF contains a complex network of 5-substituted isophthalate anions bound to Cu(II) centers, arranged in pairs within paddlewheel (or “Chinese lantern”) structure with a short Cu…Cu distance of 2.633 Å. Quite unexpectedly, the apical atom in the paddlewheel structure belongs to the carbamate carbonyl oxygen atom. Such extra coordination by the propargylcarbamate groups drastically reduces the MOF porosity, a feature that was also confirmed by BET measurements. Indeed, its surface area was determined to be low (14.5 ± 0.8 m2/g) as its total pore volume (46 mm3/g). Successively the Cu-MOF was treated with HAuCl4 with the aim of studying the ability of the propargylcarbamate functionality to capture the Au(III) ion and reduce it to Au(0) to give gold nanoparticles (AuNPs). The overall amount of gold retained by the Cu-MOF/Au was determined by AAS while the amount of gold and its oxidation state on the surface of the MOF was studied by XPS. A glassy carbon (GC) electrode was drop-casted with a Cu-MOF suspension to electrochemically characterize the material through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The performance of the modified electrodes towards nitrite oxidation was tested by CV and chronoamperometry.

Synthesis and surface characterization of metal (Mn, Ti) hexacyanoferrate electrodes

Due to the limited resources of lithium, new chemistries based on the abundant and cheap sodium and even zinc have been proposed for the battery market. Prussian Blue Analogues (PBAs) are a class of compounds which have been explored for many different applications because of their intriguing electrochemical and magnetic properties. Manganese and titanium hexacyanoferrate (MnHCF and TiHCF) belong to the class of PBAs. In this work, MnHCF and TiHCF electrodes were synthetized, cycled with cyclic voltammetry (CV) in different setups and subsequently, the surfaces were characterized with X-ray Photoelectron Spectroscopy (XPS). The setups chosen for CVs were coin cell with zinc aqueous solution for the MnHCF series, three-electrode cell and symmetric coin cell with sodium aqueous solution for the TiHCF series. The electrodes were treated with different number of cycles to evaluate the chemical changes and alterations in oxidation states during cycling.

Assessing model credibility of CT-Based finite element model to predict bone strength

Osteoporosis is one of the major causes of mortality among the elderly. Nowadays, areal bone mineral density (aBMD) is used as diagnostic criteria for osteoporosis; however, this is a moderate predictor of the femur fracture risk and does not capture the effect of some anatomical and physiological properties on the bone strength estimation. Data from past research suggest that most fragility femur fractures occur in patients with aBMD values outside the pathological range. Subject-specific finite element models derived from computed tomography data are considered better tools to non-invasively assess hip fracture risk. In particular, the Bologna Biomechanical Computed Tomography (BBCT) is an In Silico methodology that uses a subject specific FE model to predict bone strength. Different studies demonstrated that the modeling pipeline can increase predictive accuracy of osteoporosis detection and assess the efficacy of new antiresorptive drugs. However, one critical aspect that must be properly addressed before using the technology in the clinical practice, is the assessment of the model credibility. The aim of this study was to define and perform verification and uncertainty quantification analyses on the BBCT methodology following the risk-based credibility assessment framework recently proposed in the VV-40 standard. The analyses focused on the main verification tests used in computational solid mechanics: force and moment equilibrium check, mesh convergence analyses, mesh quality metrics study, evaluation of the uncertainties associated to the definition of the boundary conditions and material properties mapping. Results of these analyses showed that the FE model is correctly implemented and solved. The operation that mostly affect the model results is the material properties mapping step. This work represents an important step that, together with the ongoing clinical validation activities, will contribute to demonstrate the credibility of the BBCT methodology.

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.