Studio di metodi di preparazione e caratterizzazione di nanostrutture per la funzionalizzazione di materiali ceramici

This thesis was carried out in the context of a co-tutoring program between Centro Ceramico Bologna (Italy) and Instituto di Tecnologia Ceramica, Castellón de la Plana (Spain). The subject of the thesis is the synthesis of silver nanoparticles and at their likely decorative application in the productive process of porcelain ceramic tiles. Silver nanoparticles were chosen as a case study, because metal nanoparticles are thermally stable, and they have non-linear optical properties when nano-structured, and therefore they develop saturated colours. The nanoparticles were synthesized by chemical reduction in aqueous solution, a method chosen because of its reduced working steps and energy costs. Besides such a synthesis method uses non-expensive and non-toxic raw material. By adopting this synthesis technique, it was also possible to control the dimension and the final shape of the nanoparticles. Several syntheses were carried out during the research work, modifying the molecular weight of the reducing agent and/or the firing temperature, in order to evaluate the influence such parameters have on the Ag-nanoparticles formation. The syntheses were monitored with the use of UV-Vis spectroscopy and the average dimension as well as the morphology of the nanoparticles was analysed by SEM. From the spectroscopic data obtained from each synthesis, a kinetic study was completed, relating the progress of the reaction to the two variables (ie temperature and molecular weight of the reducing agent). The aim was finding equations that allow the establishing of a relationship between the operating conditions during the synthesis and the characteristics of the final product. The next step was finding the best method of synthesis for the decorative application. For such a purpose the amount of nanoparticles, their average particle size, the shape and the agglomeration are considered. An aqueous suspension containing the nanoparticles is then sprayed over the fired ceramic tiles and they are subsequently thermally treated in conditions similar to the industrial one. The colorimetric parameters of the obtained ceramic tiles were studied and the method proved successful, giving the ceramic tiles stable and intense colours.

Upgrading Bio-Platform Molecules in the Gas-Phase: From Levulinic Acid to Bio-Chemicals

Levulinic acid (LA) is a polyfunctional molecule obtained from biomass. Because of its structure, the United States Department of energy classified LA as one of the top 12 building block chemicals. Typically, it is valorized through chemical reduction to γ-valerolactone (GVL). It is usually done with H2 in batch systems with high H2 pressures and noble metal catalysts, making it expensive and less applicable. Therefore, alternative approaches such as catalytic transfer hydrogenation (CTH) through the Meerwein–Ponndorf–Verley (MPV) reaction over heterogeneous catalysts have been studied. This uses organic molecules (alcohols) which act as a hydride transfer agent (H-donor), to reduce molecules containing carbonyl groups. Given the stability of the intermediate, reports have shown the batch liquid-phase CTH of levulinate esters with secondary alcohols, and remarkable results (GVL yield) have been obtained over ZrO2, given the need of a Lewis acid (LASites) and base pair for CTH. However, there were no reports of the continuous gas-phase CTH of levulinate esters. Therefore, high surface area ZrO2 was tested for gas-phase CTH of methyl levulinate (ML) using ethanol, methanol and isopropanol as H-donors. Under optimized conditions with ethanol (250 ℃), the reaction is selective towards GVL (yield 70%). However, heavy carbonaceous materials over the catalyst surface progressively blocked LASites changing the chemoselectivity. The in situ regeneration of the catalyst permitted a partial recovery of the LASites and an almost total recovery of the initial catalytic behavior, proving the deactivation reversible. Tests with methanol were not promising (ML conversion 35%, GVL yield 4%). As expected, using isopropanol provided complete conversion and a GVL yield of 80%. The reaction was also tested using bioethanol derived from agricultural waste. In addition, a preliminary study was performed for the hydrogenolysis of polyols to produce bioethanol, were Pd-Fe catalyst promoted the ethanol selective (37%) hydrogenolysis of glycerol.

A chemical loop approach for methanol reforming

Over the past few years, the switch towards renewable sources for energy production is considered as necessary for the future sustainability of the world environment. Hydrogen is one of the most promising energy vectors for the stocking of low density renewable sources such as wind, biomasses and sun. The production of hydrogen by the steam-iron process could be one of the most versatile approaches useful for the employment of different reducing bio-based fuels. The steam iron process is a two-step chemical looping reaction based (i) on the reduction of an iron-based oxide with an organic compound followed by (ii) a reoxidation of the reduced solid material by water, which lead to the production of hydrogen. The overall reaction is the water oxidation of the organic fuel (gasification or reforming processes) but the inherent separation of the two semireactions allows the production of carbon-free hydrogen. In this thesis, steam-iron cycle with methanol is proposed and three different oxides with the generic formula AFe2O4 (A=Co,Ni,Fe) are compared in order to understand how the chemical properties and the structural differences can affect the productivity of the overall process. The modifications occurred in used samples are deeply investigated by the analysis of used materials. A specific study on CoFe2O4-based process using both classical and in-situ/ex-situ analysis is reported employing many characterization techniques such as FTIR spectroscopy, TEM, XRD, XPS, BET, TPR and Mössbauer spectroscopy.

Physico-chemical and microstructural properties of food dispersions

The macroscopic properties of oily food dispersions, such as rheology, mechanical strength, sensory attributes (e.g. mouth feel, texture and even flavour release) and as well as engineering properties are strongly determined by their microstructure, that is considered a key parameter in the understanding of the foods behaviour . In particular the rheological properties of these matrices are largely influenced by their processing techniques, particle size distribution and composition of ingredients. During chocolate manufacturing, mixtures of sugar, cocoa and fat are heated, cooled, pressurized and refined. These steps not only affect particle size reduction, but also break agglomerates and distribute lipid and lecithin-coated particles through the continuous phase, this considerably modify the microstructure of final chocolate. The interactions between the suspended particles and the continuous phase provide information about the existing network and consequently can be associated to the properties and characteristics of the final dispersions. Moreover since the macroscopic properties of food materials, are strongly determined by their microstructure, the evaluation and study of the microstructural characteristics, can be very important for a through understanding of the food matrices characteristics and to get detailed information on their complexity. The aim of this study was investigate the influence of formulation and each process step on the microstructural properties of: chocolate type model systems, dark milk and white chocolate types, and cocoa creams. At the same time the relationships between microstructural changes and the resulting physico-chemical properties of: chocolate type dispersions model systems dark milk and white chocolate were investigated.

A chemical-loop approach for the generation of hydrogen by means of ethanol reforming

The work investigates the feasibility of a new process aimed at the production of hydrogen with inherent separation of carbon oxides. The process consists in a cycle in which, in the first step, a mixed metal oxide is reduced by ethanol (obtained from biomasses). The reduced metal is then contacted with steam in order to split the water and sequestrating the oxygen into the looping material’s structure. The oxides used to run this thermochemical cycle, also called “steam-iron process” are mixed ferrites in the spinel structure MeFe2O4 (Me = Fe, Co, Ni or Cu). To understand the reactions involved in the anaerobic reforming of ethanol, diffuse reflectance spectroscopy (DRIFTS) was used, coupled with the mass analysis of the effluent, to study the surface composition of the ferrites during the adsorption of ethanol and its transformations during the temperature program. This study was paired with the tests on a laboratory scale plant and the characterization through various techniques such as XRD, Mössbauer spectroscopy, elemental analysis... on the materials as synthesized and at different reduction degrees In the first step it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation; magnetite was the oxide showing the slower rate of reduction by ethanol, but on the other hand it was that one which could perform the entire cycle of the process more efficiently. Still the problem of coke formation remains the greater challenge to solve.

Assessment and optimization of chemical industrial processes from a life cycle perspective

During the PhD program in chemistry, curriculum in environmental chemistry, at the University of Bologna the sustainability of industry was investigated through the application of the LCA methodology. The efforts were focused on the chemical sector in order to investigate reactions dealing with the Green Chemistry and Green Engineering principles, evaluating their sustainability in comparison with traditional pathways by a life cycle perspective. The environmental benefits associated with a reduction in the synthesis steps and the use of renewable feedstock were assessed through a holistic approach selecting two case studies with high relevance from an industrial point of view: the synthesis of acrylonitrile and the production of acrolein. The current approach wants to represent a standardized application of LCA methodology to the chemical sector, which could be extended to several case studies, and also an improvement of the current databases, since the lack of data to fill the inventories of the chemical productions represent a huge limitation, difficult to overcome and that can affects negatively the results of the studies. Results emerged from the analyses confirms that the sustainability in the chemical sector should be evaluated from a cradle-to-gate approach, considering all the stages and flows involved in each pathways in order to avoid shifting the environmental burdens from a steps to another. Moreover, if possible, LCA should be supported by other tools able to investigate the other two dimensions of sustainability represented by the social and economic issues.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

Multi-functional electrocatalysts for CO2 reduction reaction: towards the modulation of selectivity

The electrocatalytic reduction of CO2 (CO2RR) is a captivating strategy for the conversion of CO2 into fuels, to realize a carbon neutral circular economy. In the recent years, research has focused on the development of new materials and technology capable of capturing and converting CO2 into useful products. The main problem of CO2RR is given by its poor selectivity, which can lead to the formation of numerous reaction products, to the detriment of efficiencies. For this reason, the design of new electrocatalysts that selectively and efficiently reduce CO2 is a fundamental step for the future exploitation of this technology. Here we present a new class of electrocatalysts, designed with a modular approach, namely, deriving from the combination of different building blocks in a single nanostructure. With this approach it is possible to obtain materials with an innovative design and new functionalities, where the interconnections between the various components are essential to obtain a highly selective and efficient reduction of CO2, thus opening up new possibilities in the design of optimized electrocatalytic materials. By combining the unique physic-chemical properties of carbon nanostructures (CNS) with nanocrystalline metal oxides (MO), we were able to modulate the selectivity of CO2RR, with the production of formic acid and syngas at low overpotentials. The CNS have not only the task of stabilizing the MO nanoparticles, but the creation of an optimal interface between two nanostructures is able to improve the catalytic activity of the active phase of the material. While the presence of oxygen atoms in the MO creates defects that accelerate the reaction kinetics and stabilize certain reaction intermediates, selecting the reaction pathway. Finally, a part was dedicated to the study of the experimental parameters influencing the CO2RR, with the aim of improving the experimental setup in order to obtain commercial catalytic performances.

Chemical looping reforming from methane to syngas: investigation on CeO2 oxygen carrier lifetime and optimal process times

Emissions of CO2 are constantly growing since the beginning of industrial era. Interruption of the production of major emitters sectors (energy and agriculture) is not a viable way and reducing all the emission through carbon capture and storage (CCS) is not economically viable and little publicly accepted, therefore, it becomes fundamentals to take actions like retrofitting already developed infrastructure employing cleanest resources, modify the actual processes limiting the emissions, and reduce the emissions already present through direct air capture. The present thesis will deeply discuss the aspects mentioned in regard to syngas and hydrogen production since they have a central role in the market of energy and chemicals. Among the strategies discussed, greater emphasis is given to the application of looping technologies and to direct air capture processes, as they have been the main point of this work. Particularly, chemical looping methane reforming to syngas was studied with Aspen Plus thermodynamic simulations, thermogravimetric analysis characterization (TGA) and testing in a fixed bed reactor. The process was studied cyclically exploiting the redox properties of a Ce-based oxide oxygen carrier synthetized with a simple forming procedure. The two steps of the looping cycles were studied isothermally at 900 °C and 950° C with a mixture of 10 %CH4 in N2 and of 3% O2 in N2, for carrier reduction and oxidation, respectively. During the stay abroad, in collaboration with the EHT of Zurich, a CO2 capture process in presence of amine solid sorbents was investigated, studying the difference in the performance achievable with the use of contactors of different geometry. The process was studied at two concentrations (382 ppm CO2 in N2 and 5.62% CO2 in N2) and at different flow rates, to understand the dynamics of the adsorption process and to define the mass transfer limiting step.

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.