Development of a microgrid with renewable energy sources and electrochemical storage system integration

Beside the traditional paradigm of "centralized" power generation, a new concept of "distributed" generation is emerging, in which the same user becomes pro-sumer. During this transition, the Energy Storage Systems (ESS) can provide multiple services and features, which are necessary for a higher quality of the electrical system and for the optimization of non-programmable Renewable Energy Source (RES) power plants. A ESS prototype was designed, developed and integrated into a renewable energy production system in order to create a smart microgrid and consequently manage in an efficient and intelligent way the energy flow as a function of the power demand. The produced energy can be introduced into the grid, supplied to the load directly or stored in batteries. The microgrid is composed by a 7 kW wind turbine (WT) and a 17 kW photovoltaic (PV) plant are part of. The load is given by electrical utilities of a cheese factory. The ESS is composed by the following two subsystems, a Battery Energy Storage System (BESS) and a Power Control System (PCS). With the aim of sizing the ESS, a Remote Grid Analyzer (RGA) was designed, realized and connected to the wind turbine, photovoltaic plant and the switchboard. Afterwards, different electrochemical storage technologies were studied, and taking into account the load requirements present in the cheese factory, the most suitable solution was identified in the high temperatures salt Na-NiCl2 battery technology. The data acquisition from all electrical utilities provided a detailed load analysis, indicating the optimal storage size equal to a 30 kW battery system. Moreover a container was designed and realized to locate the BESS and PCS, meeting all the requirements and safety conditions. Furthermore, a smart control system was implemented in order to handle the different applications of the ESS, such as peak shaving or load levelling.

Electrochemical imaging of living cell metabolism: investigation on Warburg effect in cancer

Cancer is one of the principal causes of death in the world; almost 8.2 million of deaths were counted in 2012. Emerging evidences indicate that most of the tumors have an increased glycolytic rate and a detriment of oxidative phosphorylation to support abnormal cell proliferation; this phenomenon is known as aerobic glycolysis or Warburg effect. This switching toward glycolysis implies that cancer tissues metabolize approximately tenfold more glucose to lactate in a given time and the amount of lactate released from cancer tissues is much greater than from normal ones. In view of these fundamental discoveries alterations of the cellular metabolism should be considered a crucial hallmark of cancer. Therefore, the investigation of the metabolic differences between normal and transformed cells is important in cancer research and it might find clinical applications. The aim of the project was to investigate the cellular metabolic alterations at single cell level, by monitoring glucose and lactate, in order to provide a better insight in cancer research. For this purpose, electrochemical techniques have been applied. Enzyme-based electrode biosensors for lactate and glucose were –ad hoc- optimized within the project and used as probes for Scanning Electrochemical Microscopy (SECM). The UME biosensor manufacturing and optimization represented a consistent part of the work and a full description of the sensor preparation protocols and of the characterization methods employed is reported. This set-up (SECM used with microbiosensor probes) enabled the non-invasive study of cellular metabolism at single cell level. The knowledge of cancer cell metabolism is required to design more efficient treatment strategies.

Development and application of a thermo-hydraulic model supporting the design and the deterministic safety analysis in a sodium cooled fast reactor

Il CP-ESFR è un progetto integrato di cooperazione europeo sui reattori a sodio SFR realizzato sotto il programma quadro EURATOM 7, che unisce il contributo di venticinque partner europei. Il CP-ESFR ha l'ambizione di contribuire all'istituzione di una "solida base scientifica e tecnica per il reattore veloce refrigerato a sodio, al fine di accelerare gli sviluppi pratici per la gestione sicura dei rifiuti radioattivi a lunga vita, per migliorare le prestazioni di sicurezza, l'efficienza delle risorse e il costo-efficacia di energia nucleare al fine di garantire un sistema solido e socialmente accettabile di protezione della popolazione e dell'ambiente contro gli effetti delle radiazioni ionizzanti. " La presente tesi di laurea è un contributo allo sviluppo di modelli e metodi, basati sull’uso di codici termo-idraulici di sistema, per l’ analisi di sicurezza di reattori di IV Generazione refrigerati a metallo liquido. L'attività è stata svolta nell'ambito del progetto FP-7 PELGRIMM ed in sinergia con l’Accordo di Programma MSE-ENEA(PAR-2013). Il progetto FP7 PELGRIMM ha come obbiettivo lo sviluppo di combustibili contenenti attinidi minori 1. attraverso lo studio di due diverse forme: pellet (oggetto della presente tesi) e spherepac 2. valutandone l’impatto sul progetto del reattore CP-ESFR. La tesi propone lo sviluppo di un modello termoidraulico di sistema dei circuiti primario e intermedio del reattore con il codice RELAP5-3D© (INL, US). Tale codice, qualificato per il licenziamento dei reattori nucleari ad acqua, è stato utilizzato per valutare come variano i parametri del core del reattore rilevanti per la sicurezza (es. temperatura di camicia e di centro combustibile, temperatura del fluido refrigerante, etc.), quando il combustibile venga impiegato per “bruciare” gli attinidi minori (isotopi radioattivi a lunga vita contenuti nelle scorie nucleari). Questo ha comportato, una fase di training sul codice, sui suoi modelli e sulle sue capacità. Successivamente, lo sviluppo della nodalizzazione dell’impianto CP-ESFR, la sua qualifica, e l’analisi dei risultati ottenuti al variare della configurazione del core, del bruciamento e del tipo di combustibile impiegato (i.e. diverso arricchimento di attinidi minori). Il testo è suddiviso in sei sezioni. La prima fornisce un’introduzione allo sviluppo tecnologico dei reattori veloci, evidenzia l’ambito in cui è stata svolta questa tesi e ne definisce obbiettivi e struttura. Nella seconda sezione, viene descritto l’impianto del CP-ESFR con attenzione alla configurazione del nocciolo e al sistema primario. La terza sezione introduce il codice di sistema termico-idraulico utilizzato per le analisi e il modello sviluppato per riprodurre l’impianto. Nella sezione quattro vengono descritti: i test e le verifiche effettuate per valutare le prestazioni del modello, la qualifica della nodalizzazione, i principali modelli e le correlazioni più rilevanti per la simulazione e le configurazioni del core considerate per l’analisi dei risultati. I risultati ottenuti relativamente ai parametri di sicurezza del nocciolo in condizioni di normale funzionamento e per un transitorio selezionato sono descritti nella quinta sezione. Infine, sono riportate le conclusioni dell’attività.

Nanoparticle preparation process using novel microjet reactor technology for enhancing dissolution rates of poorly water soluble drugs

In this study a novel method MicroJet reactor technology was developed to enable the custom preparation of nanoparticles. rnDanazol/HPMCP HP50 and Gliclazide/Eudragit S100 nanoparticles were used as model systems for the investigation of effects of process parameters and microjet reactor setup on the nanoparticle properties during the microjet reactor construction. rnFollowing the feasibility study of the microjet reactor system, three different nanoparticle formulations were prepared using fenofibrate as model drug. Fenofibrate nanoparticles stabilized with poloxamer 407 (FN), fenofibrate nanoparticles in hydroxypropyl methyl cellulose phthalate (HPMCP) matrix (FHN) and fenofibrate nanoparticles in HPMCP and chitosan matrix (FHCN) were prepared under controlled precipitation using MicroJet reactor technology. Particle sizes of all the nanoparticle formulations were adjusted to 200-250 nm. rnThe changes in the experimental parameters altered the system thermodynamics resulting in the production of nanoparticles between 20-1000 nm (PDI<0.2) with high drug loading efficiencies (96.5% in 20:1 polymer:drug ratio).rnDrug releases from all nanoparticle formulations were fast and complete after 15 minutes both in FaSSIF and FeSSIF medium whereas in mucodhesiveness tests, only FHCN formulation was found to be mucoadhesive. Results of the Caco-2 studies revealed that % dose absorbed values were significantly higher (p<0.01) for FHCN in both cases where FaSSIF and FeSSIF were used as transport buffer.rn

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid–solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U.S., by using less than 0.7% of the U.S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H-2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid-solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H-2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H-2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U. S., by using less than 0.7% of the U. S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies

The redox chemistry and the related surface phase behavior of Safranine (SAF) and Janus Green B (JGB) have been studied by means of cyclic voltammetry in combination with in situ Scanning Tunneling Microscopy using HOPG (Highly Oriented Pyrolytic Graphite) and single crystalline Cu(1 0 0) as model substrates, both revealing different widths of the accessible potential windows. JGB and SAF serve as prototypical heterocyclic suppressor/leveler additives that are used for the metallization of 3D-TSVs (3D Through Silicon Vias) following a classical "leveling" concept. SAF can be considered as the reductive decomposition product of JGB that is formed at the copper/electrolyte interface upon electroplating. Both additives reveal a pronounced pH-dependent redox-chemistry with redox-transitions lying close to or even beyond the anodic limit of the copper potential window. Affected by these redox-processes are in particular the aromatic cores of those heterocycles that can be (quasi)reversibly reduced by a two electron transfer process within the potential window of copper. Therefore we identify the reduced form of those dyes as the active components for the suppressing/leveling effect in copper plating. STM data clearly shows a dye surface phase behavior that is crucially determined by its potential-dependent redox-chemistry. This will be exemplarily discussed for the SAF dye. On chloride-modified Cu(1 0 0) mono-reduced SAF forms a structurally well-defined monolayer of cationic stacking polymers. However, this coupled anion/cation layer reveals only minor suppressing capabilities with respect to the copper dissolution and deposition processes. Complete reduction of the aromatic heterocycle finally leads to the 3D precipitation of hydrophobic reaction products. 3D clusters of this SAF precipitate are discussed as the active structural motif for the suppressing effect of these dyes. (C) 2011 Elsevier Ltd. All rights reserved.

Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour

As revealed for the first time by in situ scanning tunnelling spectroscopy (STS), ferrocene-modified Si(111) substrates show ambipolar field effect transistor (FET) behaviour upon electrolyte gating.

Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes

A series of dicyanobiphenyl-cyclophanes 1-6 with various pi-backbone conformations and characteristic n-type semiconductor properties is presented. Their synthesis, optical, structural, electrochemical, spectroelectrochemical, and packing properties are investigated. The X-ray crystal structures of all n-type rods allow the systematic correlation of structural features with physical properties. In addition, the results are supported by quantum mechanical calculations based on density functional theory. A two-step reduction process is observed for all n-type rods, in which the first step is reversible. The potential gap between the reduction processes depends linearly on the cos(2) value of the torsion angle phi between the pi-systems. Similarly, optical absorption spectroscopy shows that the vertical excitation energy of the conjugation band correlates with the cos(2) value of the torsion angle phi. These correlations demonstrate that the fixed intramolecular torsion angle phi is the dominant factor determining the extent of electron delocalization in these model compounds, and that the angle phi measured in the solid-state structure is a good proxy for the molecular conformation in solution. Spectroelectrochemical investigations demonstrate that conformational rigidity is maintained even in the radical anion form. In particular, the absorption bands corresponding to the SOMO-LUMO+i transitions are shifted bathochromically, whereas the absorption bands corresponding to the HOMO-SOMO transition are shifted hypsochromically with increasing torsion angle phi.

Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes

We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1x1) electrode and covered by Au(60 nm)@SlO(2) core shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+),V(+center dot) and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of similar to 3 x 10(5), and up to 9 x 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)- catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.