Dipartimento di Chimica e Tecnologie Chimiche - Tesi di Dottorato
Permanent URI for this collectionhttp://localhost:4000/handle/10955/32
Questa collezione raccoglie le Tesi di Dottorato afferenti al Dipartimento di Chimica e Tecnologie Chimiche dell'Università della Calabria.
Browse
13 results
Search Results
Item New hybrid solar cell (СNT – RUTHENIUM DYE)(2012-12-06) Siprova, Svetlana; Versace, Carlo; De Filpo, Giovanni; Bartolino, RobertoNegli ultimi anni le applicazioni dei nanotubi di carbonio nel settore microelettronico sono notevolmente aumentate date le proprieta’ uniche. In particolare la conducibilita’ dei nanotubi fa si che essi trovino interessanti utilizzi nel settore fotovoltaico. Questo lavoro si concentra sulla progettazione di una cella solare ibrida a base di nanotubi di carbonio e dye di Rutenio. Nella prima parte sono stati studiati diversi metodi di realizzazione dello starto omogeneo di nanotubi come starto conduttivo della cella. E’ stata proposta la molecola 1-Pyrenemethanol che contiene i gruppi pirenico e ossidrilico, per creare il contatto tra i nanotubi ed il dye. Nella seconda parte del lavoro lo starto di nanotubi e’ stato formato mediante elettroforesi per single-walled nanotubes (SWNTs) e metal-organic chemical vapor deposition (CVD) per multi-walled nanotubes (MWNTs). Entrambi i metodi hanno dato la possibilita’ di creare campioni con ampia area superficiale, dai quali sono state fabbricate le celle solari. Sono state studiate determinate le dipendenze tra i fattori dei metodi e le proprieta’ delle celle prodotte.Item Novel organic optoelectronic materials(2012-11-28) Cospito, Sante; Versace, Carlo; De Simone, Bruna Carla; Bartolino, RobertoIl presente lavoro di Tesi di Dottorato di Ricerca (Scuola di Dottorato in Scienza e Tecnica "Bernardino Telesio") dal titolo "Novel Organic Optoelectronic Materials" è stato svolto all'interno dei laboratori di "Organic Optoelectronic Materials" e "New Syntheses via Organometallic Catalysis" del Dipartimento di Chimica dell'Università della Calabria. Nuovi semiconduttori organici potenzialmente impiegabili in dispositivi optoelettronici quali OLEDs, celle solari, transitors ed elettrocromici sono state progettate, sintetizzate e caratterizzate. La prima parte del lavoro ha riguardato la sintesi e la caratterizzazione di derivati di triarilammine, molecole elettron-donatrici (anodiche), da impiegare in dispositivi elettrocromici ("smart windows") per l'attenuazione della radiazione solare nel vicino infrarosso (NIR). L'intensa ed estesa banda di assorbimento nel NIR prodotta delle specie mono-ossidate ha suggerito l'impiego di queste triarilammine in dispositivi "complementari" in cui vengono utilizzate insieme a molecole elettron-accetrici (catodiche) elettrocromiche nel visibile, per un'ampia modulazione dello spettro solare. Tali sistemi sono stati dispersi all'interno di matrici polimeriche al fine di realizzare dei gel elettrocromici le cui prestazioni sono state ampiamente studiate. La risposta elettrocromica del gel è stata inoltre provata in un dispositivo plastico, dimostrandone le potenziali applicazioni campo dell'elettronica flessibile. La seconda parte del lavoro invece, ha riguardato la sintesi e lo studio delle proprietà di cristalli liquidi semiconduttori di tipo "n" (elettron-accetori) da impiegare in celle solari organiche "bulk heterojunction". Tali molecole, appartenenti alla famiglia dei viologeni estesi, hanno mostrato interessantissime proprietà mesomorfiche fortemente influenzate dalla lunghezza delle catene alchiliche ( a 9, 10 e 11 atomi di carbonio) e dell'anione utilizzato, la bis(triflimmide). Le proprietà elettrochimiche di questi composti sono state investigate sia in soluzione che nelle mesofasi. Un'efficace elettrocromismo dovuta (i) al doppio strato elettrico creato all'elettrodo degli anioni presenti e (ii) all'elevata sovrapposizione degli orbitali di frontiera dell'esteso sistema π- coniugato è stato osservato nelle fasi colonnari e smettiche in cui le molecole si sono auto-assemblate. Infine, le proprietà elettrocromiche di questi composti sono state studiate all'interno di film plastici utilizzabili in dispositivi quali i displays.Item Hybrid nanostructured fillers for polymer electrolytes in the PEM Fuel Cells(2012-11-30) Angjeli, Kristina; Versace, Carlo; Nicotera, Isabella; Bartolino, RobertoThe present thesis is focused on the development of novel nancomposite membranes, prepared by the incorporation of two-dimensional inorganic layered structures such as (i) smectite clays (synthetic and natural), (ii) graphene oxide (GO), and (iii) layered double hydroxides (LDHs) with different compositions into the polymer matrix of Nafion, for use as electrolytes in Proton Exchange Membrane fuel cells. The characteristics of the membranes were studied mainly, in terms of transport properties by NMR spectroscopy, in order to study the water dynamics inside the electrolyte membranes. For this purpose the Pulse-Field-Gradient Spin-Echo NMR (PFGSENMR) method was employed to obtain a direct measurement of water self-diffusion coefficients on the water-swelled membranes in a wide temperature range (25-140 °C). This technique together with the 1H-NMR spectral analysis and NMR spin-lattice relaxation times (T1) conducted under variable temperature. Furthermore, both pristine materials (fillers and Nafion) as well as the resulted nanocomposite membranes were characterized by a combination of X-ray diffraction, FTIR spectroscopy, thermal analysis (DTA/TGA), Raman spectroscopies and scanning electronic microscopy (SEM).Item Behavior and effects of additives in liquid crystal compounds(2011-11-03) Vivacqua, Marco; Bartolino, Roberto; Versace, Carlo; Nicoletta, Fiore P.Item Aggregate structures analysis of bitumen for the production of modified benders in asphalt industry(2013-12-02) Filippelli, Luigi; Bartolino, Roberto; Oliviero Rossi, ,CesareSince antiquity bitumen had been used as a construction material. Nowadays, most of the huge global production of bitumen each year, are functional to the roads paving industry where they are employed as binders for mineral aggregates to produce asphalt mixes. In the paving industry, a suitable bitumen should be fluid enough at to be pumpable and workable for a uniform covering of the mineral aggregates upon amalgamation. Furthermore, once the asphalt has been laid to build the roads, bitumen has to become sufficiently rigid at the highest pavement temperature to oppose rutting, depending on local climate conditions. Conversely, it must stay flexible enough at the lowest pavement temperature to resist cracking. For these purposes, additives such as polymers, acids, etc., are used to calibrate the operative range of bitumen. In addition asphalt industry is interested to reduce the costs of production, the environmental impact of the production and the safety condition for the paving workers. Bitumen is currently modeled as a dispersion of colloidal particles of asphaltenes, surrounded by a layer of stabilizing polar resins in a continuous oil phase (maltene). Although one can write a very simple definition of bitumen, its chemical composition is very complex and still not completely known. However the characterization of the bituminous materials for its convenient application, is still made by empirical standardized tests. This research project aimed to the deeper understanding of the behavior of bituminous systems, in order to correlate the macroscopic properties to the microstructure of the aggregates that constitute the bitumen colloidal network. We explored the possibility of taking advantage from chemical-physics techniques such as NMR, Rheology and AFM. In particular we have investigated the effect and overall the mechanism through which some chemical additives, already in use by paving companies, explicate their action to modulate the bitumen performances. Several samples different in nature and differently modified were analyzed. The rheological analysis, performed by the measurements under kinematic and dynamic control, helped to determine the material properties related to the structure of the system. The parameters thus obtained, being independent of the measurement conditions may be correlated with the microstructure of the sample investigated by the other techniques we used. As for NMR we exploited the spin-spin relaxation time measurement firstly to find the soften point of bituminous materials whether modified or not. As a novel approach to the understanding of the colloidal nature of the bitumen, the Inverse Laplace Transform (ILT) of the NMR spin-echo decay (T2) was applied. The ILT was used to draw the map of the macro-aggregates inside bitumen at different temperatures providing indication on the nature of the interaction between additives and the colloidal network. The efficiency of the ILT method was proved by atomic force microscopy images. As matter of fact collecting the AFM analysis, the ILT and the rheological results, we were able to describe the correlation between the aggregates at supra-molecular level inside fresh and doped bitumen. This research constituted a new inside bitumen chemistry overcoming the limits of the empirical tests to verify the efficiency of the bitumen modifiersItem Modelling of nanostructured membranes for wasterwater purification(2013-11-29) Bisignano, Federica; Bartolino, Roberto; De Luca, GiorgioThe removal of pollutants as well as the recovery of high added value molecules with low molecular weight is a current challenge in the wastewater treatment. Membrane processes can be considered as a viable option to solve these issues. In separations based membranes, high rejection of organic matter and water high permeability are two very important aspects that must be optimised. In general, the increase of the former comes at the expense of the latter because high rejection is cause of membrane fouling which in turns reduces dramatically the water permeability. Thus, membrane fouling constitutes one of the major limitations in membrane separation processes. The design of innovative materials which show high water permeability and at same time molecular rejection but with a low propensity to fouling is of fundamental relevance in this area. Mixed-matrix composite membranes where nanostructures such as Carbon Nano Tubes (CNTs) or Nano particles (NPs) are added, are receiving a huge focus since the properties of these nanostructures can confer an increase of the membrane efficiency in terms of permeability, selectivity, resistance and finally antifouling. The choice of the right nanomaterial can be highly accelerated by computational modelling. Thus, in this thesis an ab-initio modelling study in the frame of the Density Functional Theory (DFT) is carried out in order to investigate the structure-property relationships of nanostructures like CNTs and polyoxometalates NPs (POM). These nanostructures are used in the preparation of composite membranes in the frame of BioNexGen project [1] with the aim to propose novel membranes to be used in bioreactor for industrial waste water treatment. In particular, the rejection of CNTs towards organic solutes with low molecular weight coming from industrial waste water such as cosmetic, textile and oil olive was analysed in conjunction to the optimization of water permeability in CNTs. Also, the adsorption of POMs on polymeric membrane surface was analysed in order to understand if an efficient antifouling property can be imparted to the membranes by adding these NPs which possess excellent antibacterial and oxidants properties. While nanotube permeability has been extensively studied in both experimental and modelling works resulting in orders of magnitude water flow enhancements for tube diameters in the reverse osmosis and nanofiltration range [2], less work has been done on CNT selectivity of small organic solutes. Precise control of the CNTs synthesis allows for fine-tuning of the outer and inner diameters in the case of single- and multi-wall carbon nanotubes (SWNTs and MWNTs, respectively), offering the possibility of controlling their selectivity toward small solutes. In this thesis a modelling study was, therefore, addressed to define the optimal CNT internal diameter that should be used in order to achieve a total rejection of several target compounds very difficult to separate. Three novel algorithms [3, 4] were implemented during the thesis for reach the aforementioned objective. These algorithms do not make use of any adjustable parameters (i.e. fitting parameters) being based on geometry optimizations carried out in the frame of high level of quantum approach (DFT) and topological analysis of the considered systems. In addition, the CNTs geometrical characteristics should be optimized in order to get the best compromise between permeability and rejection. The functionalizing of the nanotubes tip with specific functional groups capable of hindering the passage of solutes while allowing water molecules to flow has been suggested as a solution to this problem [5, 6]. Thus, a theoretical study of CNT-composite membranes was carried out in this work with the aim of optimizing the CNTs tip, through their functionalization, to maximise both water permeability and solutes selectivity. This study is the basis of the third implemented algorithm [7]. Concerning the membrane fouling, the analysis of the adsorption of antibacterial anionic NPs (i.e. POM) on the surface of polymeric membranes was carried out in this thesis in order to achieve an optimal adsorption of these NPs. Noncovalent interactions between POM and commercial surfactants, used in polymer membrane preparations, were evaluated. Anionic POMs are in fact promising antibacterial agents [8], therefore, an efficient exchange with the bromide ions, used to counterbalance the positive charge of the commercial surfactants, would allow to increase the efficiency of the membrane by reducing the organic and bio fouling. In order to achieve this result, besides the aforementioned POM-surfactants noncovalent interactions the electronic hydration energy of POM and bromide anions was also evaluated in order to predict the probable exchange of these anions on the polymer surface. The conclusions of this thesis are achieved by using only ab-initio methods thus the results can be considered quite generals and homogeneous, free from empirical or fitting parameters. A validation of the theoretically prediction is provided concerning the POM-bromide exchange by means of an ad hoc designed experiment. The experimental results are in agreement with the theoretically predictionsItem NMR in different partially ordered media: a route for structure, order and conformation of small organic compounds(2013-11-20) Di Pietro, Marica Erica; Bartolino, Roberto; Merlet, DenisNMR spectroscopy in weakly and highly orienting media is used as a route for dealing with orientational, positional, structural and conformational problems of a variety of small rigid and flexible organic molecules in solution. First, the very weak orientational order of a quasi-spherical molecule dissolved in a nematic phase is exploited for exploring the role of the different contributions to the observed dipolar coupling. In such a limit condition, a predominant effect of the non-rigid reorientationvibration coupling term emerges. Then, NMR data obtained from small rigid probes dissolved in smectic solvents are combined with a statistical thermodynamic density functional theory, in order to measure the positional order parameters of both solutes and solvent. The methodology gives good results when applied to a conventional smectic A liquid crystal and to the more delicate case of an interdigitated smectic Ad phase. The strategy is subsequently extended to the investigation of structure, order and conformational equilibrium of flexible bioactive or biomimetic molecules dissolved in various partially ordered NMR solvents. A first experimental and theoretical study is presented on the symmetric single-rotor molecule of biphenyl dissolved in a thermotropic liquid crystal. This test-case indicates molecular dynamics simulations are a promising tool for estimating a set of dipolar couplings of a solute in a thermotropic solvent, to be used as starting set of parameters in a standard operator-mediated NMR spectral analysis. Then, we report the conformational study of some single- and two-rotor nonsteroidal anti-inflammatory drugs, belonging to the families of salicylates and profens, dissolved in weakly orienting chiral nematic PBLG phases. A new pulse sequence, the Gradient Encoded heTeronuclear 1H-19F SElective ReFocusing NMR experiment (GET-SERF), is proposed here for the trivial edition of all 1H-19F couplings in one single NMR experiment, for a given fluorine atom. Starting from homo- and heteronuclear dipolar couplings, difficult to extract in thermotropic solvents because of a too complex spectral analysis, the torsional distributions of such molecules can be satisfactory described by the Additive Potential model combined with the Direct Probability Description of the torsional distribution in terms of Gaussian functions (AP-DPD approach). Finally, the conformational and orientational study of two stilbenoids displaying cooperative torsions is discussed in both a highly and weakly ordering liquid crystal phase. This comparative study allows to draw some conclusions on reliability, accuracy and accessibility of desired data in the two phases. Overall, this work proves NMR in liquid crystals is a flexible and meaningful tool for studying order, structure and conformation and it can greatly benefit from the availability of several aligning media inducing a different degree of order.Item Gallium coordination compounds as multifunctional materials. Synthesis, characterization and properties(2006-11-30) De Franco, Irene; Ghedini, Mauro; Longeri, MarcelloItem Solar control solid organic electrochromic films(2006-11-30) De Benedittis, Maurizio; De Simone, Bruna Clara; Longeri, M.Item Optical and electrical properties of polymer dispersed nanoparticles(2008-11-28) Tyurin, Alexander; Chidichimo, G.; Versace, C.