Catalytic reduction of levulinic acid derivatives to bio-fuel components

Levulinic Acid and its esters are polyfunctional molecules obtained by biomass conversion. The most investigated strategy for the valorization of LA is its hydrogenation towards fuel additives, solvents and other added-value bio-based chemicals and, in this context, heterogeneous and homogeneous catalysts are widely used. Most commonly, it is typically performed with molecular hydrogen (H2) in batch systems, with high H2 pressures and noble metal catalysts. Several works reported the batch liquid-phase hydrogenation of LA and its esters by heterogenous catalysts which contained support with Brønsted acidity in order to obtain valeric acid and its esters. Furthermore, bimetallic and monometallic systems composed by both a metal for hydrogen activation and a promoter were demonstrated to be suitable catalysts for reduction of carboxylic group. However, there were no studies in the literature reporting the hydrogenation of alkyl levulinates to 1-pentanol (1-PAO). Therefore, bimetallic and monometallic catalysts were tested for one-pot hydrogenation of methyl levulinate to 1-PAO. Re-based catalysts were investigated, this way proving the crucial role of the support for promoting the ring-opening of GVL and its consecutive reduction to valeric compounds. All the reactions were performed in neat without the need of any additional solvents. In these conditions, bimetallic Re-Ru-O/HZSM-5 afforded methyl valerate and valeric acid (VA) with a productivity of 512 mmol gmetal-1 h-1, one of the highest reported in literature to date. Rhenium can also promote the reduction of valeric acid/esters to PV through the formation of 1-pentanol and its efficient esterification/transesterification with the starting material. However, it was proved that Re-based catalysts may undergo leaching of active phase in presence of carboxylic acids, especially by working in neat with VA. Furthermore, the over-reduction of rhenium affects catalytic performance, suggesting not only that a pre-reduction step is unnecessary but also that it could be detrimental for catalyst’s activity.

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.

Design, synthesis and photovoltaic properties of some thiophene-based conjugated polymers for organic solar cells

The current issue of the resource of energy combined with the tendency to give a green footprint to our lifestyle have prompted the research to focus the attention on alternative sources with great strides in the optimization of polymeric photovoltaic devices. The research work described in this dissertation consists in the study of different semiconducting π-conjugated materials based on polythiophenes (Chapter I). In detail, the GRIM polymerization was deepened defining the synthetic conditions to obtain regioregular poly(3-alkylthiophene) (Chapter II). Since the use of symmetrical monomers functionalized with oxygen atom(s) allows to adopt easy synthesis leading to performing materials, disubstituted poly(3,4-dialkoxythiophene)s were successfully prepared, characterized and tested as photoactive materials in solar cells (Chapter III). A “green” resource of energy should be employed through sustainable devices and, for this purpose, the research work was continued on the synthesis of thiophene derivatives soluble in eco-friendly solvents. To make this possible, the photoactive layer was completely tailored starting from the electron-acceptor material. A fullerene derivative soluble in alcohols was successfully synthetized and adopted for the realization of the new devices (Chapter IV). New water/alcohol soluble electron-donor materials with different functional groups were prepared and their properties were compared (Chapter V). Once found the best ionic functional group, a new double-cable material was synthetized optimizing the surface area between the different materials (Chapter VI). Finally, other water/alcohol soluble materials were synthetized, characterized and used as cathode interlayers in eco-friendly devices (Chapter VII). In this work, all prepared materials were characterized by spectroscopy analyses, gel permeation chromatography and thermal analyses. Cyclic voltammetry, X-ray diffraction, atomic force microscopy and external quantum efficiency were used to investigate some peculiar aspects.

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.

Innovative electrospun nanofibers for improving delamination resistance and damping of CFRP laminates

Carbon Fiber Reinforced Polymers (CFRPs) are well renowned for their excellent mechanical properties, superior strength-to-weight characteristics, low thermal expansion coefficient, and fatigue resistance over any conventional polymer or metal. Due to the high stiffness of carbon fibers and thermosetting matrix, CFRP laminates may display some drawbacks, limiting their use in specific applications. Indeed, the overall laminate stiffness may lead to structural problems arising from their laminar structure, which makes them susceptible to structural failure by delamination. Moreover, such stiffness given by the constituents makes them poor at damping vibration, making the component more sensitive to noise and leading, at times, to delamination triggering. Nanofibrous mat interleaving is a smart way to increase the interlaminar fracture toughness: the use of thermoplastic polymers, such as poly(ε- caprolactone) (PCL) and polyamides (Nylons), as nonwovens are common and well established. Here, in this PhD thesis, a new method for the production of rubber-rich nanofibrous mats is presented. The use of rubbery nanofibers blended with PCL, widely reported in the literature, was used as matrix tougheners, processing DCB test results by evaluating Acoustic Emissions (AE). Moreover, water-soluble electrospun polyethylene oxide (PEO) nanofibers were proposed as an innovative method for reinforcing layers and hindering delamination in epoxy-based CFRP laminates. A nano-modified CFRP was then aged in water for 1 month and its delamination behaviour compared with the ones of the commercial laminate. A comprehensive study on the use of nanofibers with high rubber content, blended with a crystalline counterpart, as enhancers of the interlaminar properties were then investigated. Finally, PEO, PCL, and Nylon 66 nanofibers, plain or reinforced with Graphene (G), were integrated into epoxy-matrix CFRP to evaluate the effect of polymers and polymers + G on the laminate mechanical properties.

Study and development of BaCe0.65Zr0.20Y0.1503-Δ (BCZY) – Gd0.2Ce0.8O2-Δ (GDC) dense ceramic membranes sysyem for high temperature H2 purification

The first main conclusion drawn from this dissertation concerns the amount of Pt deposited on the asymmetric layer of membrane produced by tape casting porosity shaping method. Three different amounts were investigated (0.15, 1.5 and 4.5 mg cm-2 ). The most optimal performance, based on H2 permeation performances, was attained when 1.5 mg cm-2 of Pt was deposited on the porous layer, resulting in a 0.642 mL min-1 cm-2 permeated H2 when 80% H2 in He was employed as the feed. Pt deposition method is influenced by the concentration of the Pt precursor, which results in different morphology of the catalyst. The second development focused on further optimization on tape casting membranes concerning the solvent employed for the Pt catalyst deposition. The same concentration of Pt was employed, depositing 1.5 mg cm-2 on the porous side of the membrane, but a mixture of acetone and water was employed as solvent. This mixture allowed the suppression of effects leading to poorly dispersed particles. As a result, it was possible to achieve 0.74 mL min-1 cm-2 at 750°C with 50% H2 in He. Lastly, first-ever permeation performance measurements into an innovative ceramic membrane type for hydrogen separation was investigated. In-depth research was done on a group of hierarchically-structured BaCe0.65Zr0.20Y0.15O3-δ(BCZY) - Gd0.2Ce0.8O2-δ(GDC) membranes produced by freeze casting porosity shaping method. Membranes were investigated observing the effect of deposition solvent and the effect of porous layer thickness. Employing a mixture of Acetone and water resulted in better hydrogen permeation at temperatures (T > 650°C), reaching 0.26 mL min-1 cm-2 at 750°C with 50% H2 in He. The reduction of porous layer thickness led to a hydrogen flow of 0.33 mL min-1 cm-2 , at 750°C with 50% H2 in He.

Investigation on the role of polymeric ligands in heterogeneous nanocatalysis towards the development of hybrid metal-polymer catalysts

The relationship between catalytic properties and the nature of the active phase is well-established, with increased presence typically leading to enhanced catalysis. However, the costs associated with acquiring and processing these metals can become economically and environmentally unsustainable for global industries. Thus, there is potential for a paradigm shift towards utilizing polymeric ligands or other polymeric systems to modulate and enhance catalytic performance. This alternative approach has the potential to reduce the requisite amount of active phase while preserving effective catalytic activity. Such a strategy could yield substantial benefits from both economic and environmental perspectives. The primary objective of this research is to examine the influence of polymeric hydro-soluble ligands on the final properties, such as size and dispersion of the active phase, as well as the catalytic activity, encompassing conversion, selectivity towards desired products, and stability, of colloidal gold nanoparticles supported on active carbon. The goal is to elucidate the impact of polymers systematically, offering a toolbox for fine-tuning catalytic performances from the initial stages of catalyst design. Moreover, investigating the potential to augment conversion and selectivity in specific reactions through tailored polymeric ligands holds promise for reshaping catalyst preparation methodologies, thereby fostering the development of more economically sustainable materials.

Influence of additives on the performance of a PVDF membrane

The field of use of membranes is wide and ranges from the automotive industry to biomedical uses. Many formulations and compositions find a niche where they are able to improve efficiency, running cost and quality of the product. The aim of this research is to expand GVS’s product portfolio introducing a new membrane formulation. A series of additives were researched and evaluated, adding them to the membrane solutions, which were then cast and characterised using techniques like Scanning Electron Microscopy (SEM), poroscopy, FT-IT ATR and measurements like Water Break Through (WBT), Air Flow (AF), thickness. This study ultimately focused on one additive, which effect on the membranes was studied in various compositions. Interesting insights were also collected on the stability of the polymer solutions over time, which was found to change the membrane properties significantly, mainly affecting airflow and water breakthrough. Properties of the membranes were studied to find possible correlations to the amount of additive. The additive seems however to change the membrane porometry considerably depending on the time of immersion in the water bath. A new procedure to yield uniform unsupported polymeric membranes for tensile tests was developed. The additive was found to reduce elongation at break and decrease tensile strength of the membranes, possibly hinting toward plasticization of the product.

Sintesi di compositi nanostrutturati a base di TiO2 per la depurazione delle acque

Lo scopo di questo lavoro di tesi consiste nella realizzazione di fotocatalizzatori a base di nano-TiO2 per potenziali applicazioni nel campo della depurazione delle acque reflue. Nello specifico sono stati sintetizzati nanocompositi accoppiando nano-TiO2 a due materiali grafitici: ossido di grafene (GO), tramite ultrasonicazione (TGO) e nitruro di carbonio grafitico (g-C3N4), attraverso due tecniche: ultrasonicazione e polimerizzazione termica in situ. Per i compositi TGO lo studio relativo alla sintesi è stato rivolto all’ottimizzazione della percentuale in peso di GO. Per i compositi a base di g-C3N4 lo scopo è stato quello di valutare quale dei due metodi di sintesi fosse il più efficace. I materiali ottenuti sono stati caratterizzati dal punto di vista chimico-fisico (DLS-ELS, XRD, Band Gap, BET, SEM, FT-IR, TGA-DSC) e funzionale. La caratterizzazione funzionale è stata eseguita per valutare le prestazioni fotocatalitiche dei fotocatalizzatori nanocompositi utilizzando, come reazione modello, la fotodegradazione di Rodamina B, sotto luce UV e solare. I risultati hanno messo in luce che la percentuale ottimale di GO, nei compositi TGO, è pari al 16%. Inoltre, è stato osservato un effetto sinergico tra TiO2 e GO dove i nanocompositi TGO hanno mostrato maggiore attività fotocatalitiche rispetto alla singola TiO2. I dati fotocatalitici hanno evidenziato che il metodo ottimale per la preparazione dei compositi a base di g-C3N4 e TiO2, è la polimerizzazione termica in situ a 500°C.

Computational investigation of a stereoselective synthesis of atropisomeric hydrazides possessing an N–N stereogenic axis

Axially chiral substrates are an interesting and widely studied class of compounds as they can be found in bioactive natural products and are employed as functional materials or as ligands in asymmetric catalytic processes. One branch of this family is the well-known world of the atropisomers. Among them, atropisomeric compounds possessing an N–N stereogenic axis are one truthfully fascinating system but not completely understood yet. In this thesis, we computationally investigated the mechanism of the diastereoselective formation of the N – N chiral axis of a hydrazide under asymmetric phase transfer catalytic conditions. Moreover, during this study, torsional barriers have been calculated for both the reagent and the product at the density functional theory (DFT). These values turned out to suitably match the experimental values and observations. Finally, Electronic Circular Dichroism (ECD) spectra have been simulated in order to assign the chiral absolute configuration to the products.

Valutazione degli impatti ambientali relativi alla valorizzazione delle sanse di oliva in una prospettiva di ciclo di vita

Nel presente elaborato di tesi la metodologia Life Cycle Assessment (che in accordo con le norme ISO 14040-44 permette di quantificare i potenziali impatti sull’ambiente associati ad un bene o servizio lungo tutto il suo ciclo di vita) è applicata a processi appartenenti al settore agro-industriale, con particolare riguardo alla valorizzazione dei coprodotti della filiera olivicola olearia. Nello specifico vengono descritti i risultati di un’analisi del ciclo di vita condotta sul processo di valorizzazione delle sanse di oliva operata dalla Società Agricola A.R.T.E, che ha sede in Puglia. In questo processo, la sansa di olive è trattata mediante digestione anaerobica che permette la produzione di energia elettrica e di un digestato, stabilizzato e utilizzato come ammendante. Il processo analizzato si pone in alternativa sia al metodo di produzione che dà origine a sanse trifasiche, sia allo spandimento delle sanse su suolo agricolo, confrontati in termini di impronta di carbonio. Inoltre nello studio sono state confrontate diverse tecnologie di upgrading di biogas a biometano per valutare quale risulta essere ambientalmente preferibile e potenzialmente installabile nell’azienda A.R.T.E. Il sistema analizzato risulta un'alternativa complessivamente preferibile, da un punto di vista ambientale, sia al metodo di produzione che dà origine a sanse trifasiche, sia allo spandimento delle sanse su suolo agricolo. Il credito ambientale conseguibile mediante il recupero energetico dal biogas prodotto dalla digestione anaerobica delle sanse bifasiche e la produzione di un digestato stabile permettono un beneficio ambientale che controbilancia l’emissione di CO2 attribuibile all’intero sistema. Inoltre lo studio ha permesso una stima di quale tecnologia di raffinazione del biogas a biometano sia potenzialmente installabile nell’azienda A.R.T.E. I risultati mostrano che la tecnologia separazione a membrana risulta meno impattante rispetto alle altre tecnologie di upgrading.

Studio computazionale DFT e TD-DFT dei dimeri della Rodamina-B

L’oggetto di questo elaborato è lo studio computazionale, a livello della teoria del funzionale della densità (DFT) e della sua formulazione dipendente dal tempo (TD-DFT), dei dimeri della molecola di rodamina-B, parallelo allo sviluppo di una procedura di tuning ottimale del funzionale CAM-B3LYP. Questa molecola, che assume notevole rilevanza nei sistemi light harvesting grazie alle sue proprietà fotochimiche di emissione nel visibile, è impiegata nella sintesi di nanoparticelle (NPs) fluorescenti in ambito di diagnostica medica e bio-imaging, che sfruttano il fenomeno di trasferimento di energia per risonanza (FRET). Per via della notevole importanza che questa molecola riveste nell’ambito della fotochimica, essa è stata oggetto di esperimenti del gruppo di ricerca del laboratorio di biofotonica e farmacologia “Nanochemistry and Bioimaging”, che collabora con il gruppo di chimica computazionale dell’area chimico/fisica del Dipartimento. La dimerizzazione della rodamina all’interno delle NPs può innescare canali di self-quenching che abbassano la resa quantica di fluorescenza, pregiudicando l’efficienza dei dispositivi: l’obiettivo dello studio è la caratterizzazione dei dimeri, in solventi e con controioni diversi, impiegando dei modelli molecolari, per identificarne le specie più stabili e descrivere la fotofisica degli stati elettronici eccitati. Il carattere generalmente charge-transfer (CT) di questi stati elettronici richiede un “tuning ottimale” della metodologia computazionale DFT/TD-DFT per una descrizione quantitativa accurata.

Modeling Ultrafast Spectroscopy of the NADH Dimer: From UV-VIS to X-rays

Ultrafast pump-probe spectroscopy is a conceptually simple and versatile tool for resolving photoinduced dynamics in molecular systems. Due to the fast development of new experimental setups, such as synchrotron light sources and X-ray free electron lasers (XFEL), new spectral windows are becoming accessible. On the one hand, these sources have enabled scientist to access faster and faster time scales and to reach unprecedent insights into dynamical properties of matter. On the other hand, the complementarity of well-developed and novel techniques allows to study the same physical process from different points of views, integrating the advantages and overcoming the limitations of each approach. In this context, it is highly desirable to reach a clear understanding of which type of spectroscopy is more suited to capture a certain facade of a given photo-induced process, that is, to establish a correlation between the process to be unraveled and the technique to be used. In this thesis, I will show how computational spectroscopy can be a tool to establish such a correlation. I will study a specific process, which is the ultrafast energy transfer in the nicotinamide adenine dinucleotide dimer (NADH). This process will be observed in different spectral windows (from UV-VIS to X-rays), accessing the ability of different spectroscopic techniques to unravel the system evolution by means of state-of-the-art theoretical models and methodologies. The comparison of different spectroscopic simulations will demonstrate their complementarity, eventually allowing to identify the type of spectroscopy that is best suited to resolve the ultrafast energy transfer.

"Assisted factorial experimental design" per l'ottimizzazione della determinazione di benzene ematico in gc-fid

La quantificazione del benzene ematico è un tema di grande interesse nell'ambito della tossicologia occupazionale. La determinazione dell'analita, estratto nello spazio di testa di un vial, è eseguita mediante l'utilizzo di un gascromatografo con rilevatore a ionizzazione di fiamma (GC-FID). Si è cercato di ottimizzare il processo di estrazione del benzene dal sangue allo spazio di testa ed il successivo trasferimento dell'analita nella colonna cromatografica, mediante l'applicazione di un disegno sperimentale fattoriale a tre fattori e due livelli (DoE). I fattori individuati per impostare il piano sperimentale sono stati: variazione della temperatura di incubazione (A) del vial contenente il campione di sangue, pH del campione (B), modulato mediante aggiunta di una soluzione di H2SO4 e forza ionica (C), regolata mediante una soluzione acquosa di NaCl. I livelli scelti per ciascuna variabile sono stati: per A 40 e 60 °C; per B pH naturale del campione e pH a seguito dell'aggiunta di 1 mL di H2SO4 1.8 M; per C FI naturale del campione e FI dovuta all'aggiunta di una soluzione acquosa di sodio cloruro (5 g/L). Dall'analisi dei risultati forniti dal DoE, si è osservato che A, B e C hanno effetti tra loro contrastanti, per questo motivo non sembra essere vantaggioso combinare variabili differenti. In compenso, sia l'aumento di temperatura che l'aggiunta di acido solforico portano a significativi miglioramenti nell'estrazione di benzene dal sangue. Tra i tre trattamenti risulta essere B quello più efficace, motivo per il quale si ritiene che l'aggiunta di una soluzione acquosa di H2SO4 al campione di sangue porti ad una maggiore sensibilità e risoluzione strumentale. Sicuramente la sensibilità del metodo elaborato non può essere paragonata alle tradizionali determinazioni con spettrometro di massa, ma si ritiene possa essere sufficientemente soddisfacente per valutare l'esposizione a benzene dei lavoratori a rischio e come analisi di screening rapida ed economica.

Sviluppo ed ingegnerizzazione di nuovi sistemi ibridi a base di nanoparticelle inorganiche e bio-tensioattivi

In questo lavoro di tesi è stata investigata la sintesi di compositi a base di nano particelle di biossido di titanio rivestite da un bio-tensioattivo naturale. Il noto fotocatalizzatore (Nano-TiO2) è stato accoppiato ad un bio-tensioattivo dalle riconosciute proprietà antibatteriche, antivirali e anti-tumorali per ottenere un materiale composito multifunzionale. Diverse opzioni di design sono state investigate e la sintesi ottimizzata attraverso una caratterizzazione sistematica dei materiali prodotti, sia sulle sospensioni (DLS, ELS, TEM) sia sui prodotti granulati e calcinati (XRD, FT-IR, SEM, UV-Vis., BET). Per comprendere il ruolo del bio-tensioattivo e i potenziali effetti sinergici che il materiale composito potesse generare, si sono effettuate diverse caratterizzazioni funzionali testando il materiale per la realizzazione di nano-fasi fotocatalitiche da impiegare in processi di adsorbimento/degradazione di inquinanti acquosi, per la realizzazione di rivestimenti tessili antibatterici e come composito utile per l’assorbimento di metalli pesanti.