EFFECTS OF ADDING LANTHANUM TO Ni/ZrO2 CATALYSTS ON ETHANOL STEAM REFORMING

EFFECTS OF ADDING LANTHANUM TO Ni/ZrO2 CATALYSTS ON ETHANOL STEAM REFORMING. The catalytic performance of Ni/ZrO2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting; with the support, due to the higher dispersion effect. The best catalytic performance at 450 degrees C was found for the Ni/2LZ catalyst, which exhibited an effluent gaseous mixture with the highest H-2 yield.

Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

Carbon supported Pt-Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 degrees C and 90 degrees C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt3Sn1/C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Borohydride electrooxidation on Au and Pt electrodes

Direct borohydride fuel cells (DBFCs) are attractive energy generators for powering portable electronic devices, mainly due to their high energy density and number of electrons per borohydride ion. However, the lack of a highly efficient electrocatalyst for the borohydride oxidation reaction limits the performance of these devices. The most commonly studied electrocatalysts for this reaction are composed of gold and platinum. Nevertheless, for these metals, the borohydride electrooxidation reaction mechanism (BOR) is not completely understood, and the total oxidation reaction, involving eight electrons per BH4- species, competes with parallel reactions, with a lower number of exchanged electrons and/or with heterogeneous chemical hydrolysis. Considering the above-mentioned issues, this work presents recent advances in the knowledge of the BOR pathways on polycrystalline (bulk) Au and Pt electrocatalysts. It presents the studies of the BOR reaction on Au and Pt electrodes using in situ Fourier Transform Infrared Spectroscopy (FUR), and on-line Differential Electrochemical Mass Spectrometry (DEMS). The spectroscopic and spectrometric data provided physical evidence of intermediate species and the formation of H-2 in the course of the BOR as a function of the electrode potential. These results enabled to advance in the knowledge about the BOR pathways on Au and Pt electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

Self-potential signals from an analog biogeobattery mode

A tank experiment was conducted to check if self-potential (SP) signals can be generated when buried organic matter is wire-connected to a near-surface, oxygen-rich, sediment layer. This experiment demonstrated that once wired, there was a flux of electrons (hence an electric current) between the lower and upper layers of the sandbox with the system responding as a large-scale microbial fuel cell (a type of bioelectrochemical system). An electric current was generated by this process in the wire and the SP method was used to monitor the associated electric potential distribution at the top of the tank.. The electric field was controlled by the flux of electrons through the wire, the oxidation of the organic matter, the reduction of oxygen used as a terminal electron acceptor, and the distribution of the DC resistivity in the tank. The current density through the wire was limited by the availability of oxygen and not by the oxidation of the organic matter. This laboratory experiment incorporated key elements of the biogeobattery observed in some organic-rich contaminant plumes. This analogy includes the generation of SP signals associated with a flux of electrons, the capacity of buried organic matter in sustaining anodic reactions, network resistance connecting terminal redox reactions spatially separated in space, and the existence of anodic secondary coupled reactions. A resistivity tomogram of the tank, after almost a year in operation, suggests that oxidative processes triggered by this geobattery can be imaged with this method to determine the radius of influence of the bioelectrochemical system.

Her2p molecular modeling, mutant analysis and intramitochondrial localization

Bacterial GatCAB amidotransferases are responsible for the transamidation of mischarged glutamyl-tRNA(Gln) into glutaminyl-tRNA(Gln). Mitochondria matrix also has a multienzymatic complex necessary for the transamidation of glutamyl-tRNA(Gln). Gtf1p, Her2p and Pet112p are the constituents of mitochondrial GatFAB amidotransferase complex. Her2p is subunit A of GatFAB complex, while Gtf1p is subunit F, a connector protein between Pet112p (subunit B) and Her2p. Here we evaluate through molecular modeling and amino acid correlation analysis the HER2 protein family. Localization studies indicated that Her2p is predominantly localized in the mitochondrial outer membrane, but it is also located in the mitochondrial matrix where together with Pet112p and Gtf1p constitutes the GatFAB complex. Finally, HER2 random mutagenesis unveiled important residues that provide thermo stability for the complex and are differently suppressed by overexpression of GTF1 or PET112. For instance, her2/ts11 mutant showed its fermentative growth impaired, and poorly rescued by GTF1 indicating that Her2p unknown function in the mitochondria outer membrane affects cell viability.

Electrogeneration of platinum nanoparticles in a matrix of dendrimer-carbon nanotubes

Hybrid materials with enhanced properties can now be obtained by combining nanomaterials such as carbon nanotubes and metallic nanoparticles, where the main challenge is to control fabrication conditions. In this study, we demonstrate that platinum nanoparticles (PtNps) can be electrogenerated within layer-by-layer (LbL) films of polyamidoamine (PAMAM) dendrimers and single-walled carbon nanotubes (SWCNTs), which serve as stabilizing matrices. The advantages of the possible control through electrogeneration were demonstrated with a homogeneous distribution of PtNps over the entire surface of the PAMAM/SWCNT LbL films, whose electroactive sites could be mapped using magnetic force microscopy. The Pt-containing films were used as catalysts for hydrogen peroxide reduction, with a decrease in the reduction potential of 60 mV compared to a Pt film deposited onto bare ITO. By analyzing the mechanisms responsible for hydrogen peroxide reduction, we ascribed the enhanced catalytic activity to synergistic effects between platinum and carbon in the LbL films, which are promising for sensing and fuel cell applications.

Ottimizzazione dei processi depurativi di reflui ad elevato carico organico a fini di recupero energetico

L’attuale condizione che caratterizza il settore energetico richiede un necessario processo di riconversione che, oltre a favorire il risparmio energetico, riduca la dipendenza dai combustibili fossili ed accresca l’impiego di fonti energetiche rinnovabili, dando un contributo fondamentale alla riduzione delle emissioni di gas serra come diversi accordi internazionali richiedono. Si rende pertanto necessario accelerare i processi che da alcuni anni stanno favorendo l’utilizzo di energia da fonti rinnovabili. Tra queste, le fonti legate ai processi di trattamento biologico dei reflui stanno avendo un interessante sviluppo. Esistono numerosi processi biologici che consentono la produzione di energia in maniera indiretta, quali ad esempio i processi di digestione anaerobica finalizzati alla produzione di biogas e/o produzione biologica di idrogeno. In tale contesto si inserisce la tecnologia delle Microbial Fuel Cell, che consente la produzione diretta di energia elettrica, finalizzata al recupero energetico inteso al miglioramento dell’efficienza energetica e alla riduzione dei costi d’esercizio di impianti di trattamento biologico dei reflui. Il presente lavoro di Tesi di Dottorato sperimentale, svoltosi in collaborazione al laboratorio PROT.-IDR. della sede ENEA di Bologna, riporta i risultati dell’attività di ricerca condotta su una MFC (Microbial Fuel Cell) a doppio stadio biologico per il trattamento di reflui ad elevato carico organico e produzione continua di energia elettrica. E’ stata provata l’applicabilità della MFC con entrambi i comparti biotici utilizzando elettrodi di grafite non trattata ottenendo, con un carico organico in ingresso di circa 9 gd-1, valori di potenza massima prodotta che si attestano su 74 mWm-2, corrente elettrica massima generata di 175 mAm-2 ad una tensione di 421 mV, ed una conversione di COD in elettricità pari a 1,2 gCODm-2d-1. I risultati sono stati molto positivi per quanto riguarda le prestazioni depurative ottenute dalla MFC. L’efficienza di depurazione misurata ha raggiunto un valore massimo del 98% di rimozione del COD in ingresso, mentre e la concentrazione di azoto ammoniacale nell’effluente raccolto all’uscita del sedimentatore è sempre stata inferiore a 1 mgN-NH4+l-1. Tra gli obiettivi posti all’inizio della sperimentazione si è rivelata di notevole interesse la valutazione del possibile utilizzo della MFC come sistema per il monitoraggio on-line del COD e degli acidi grassi volatili (VFA) prodotti all’interno di un digestore anaerobico, attraverso la definizione di una correlazione tra i dati elettrici registrati in continuo e le concentrazioni di CODanaer e VFA misurate in diversi periodi della sperimentazione. L’analisi DGGE della biomassa catodica ha fornito uno strumento analitico utile allo studio della diversità della comunità microbica sospesa ed adesa al catodo e ha confermato la forte similarità delle specie batteriche riconosciute nei campioni analizzati. In particolare, le bande di sequenziamento ottenute sono affiliate ai gruppi batterici Firmicutes, -Proteobacteria,  -Proteobacteria, -Proteobacteria e Bacteroidetes. Da quanto emerso dalla sperimentazione condotta si può pertanto concludere che ad oggi le MFC sono in fase di evoluzione rispetto ai primi prototipi utilizzati per lo studio delle comunità microbiali e per la comprensione dei meccanismi di trasferimento elettronico. Sfruttarne la potenza prodotta in maniera commerciale diviene una grande sfida per il futuro, ed è opinione comune che le prime applicazioni pratiche delle MFC saranno come fonte di recupero energetico per i dispositivi utilizzati per il monitoraggio dell’ambiente e per il trattamento delle acque reflue.

Optical Microring Resonators based on ion-implanted LiNbO3 ridge waveguides

The growing interest for Integrated Optics for sensing, telecommunications and even electronics is driving research to find solutions to the new challenges issued by a more and more fast, connected and smart world. This thesis deals with the design, the fabrication and the characterisation of the first prototypes of Microring Resonators realised using ion implanted Lithium Niobate (LiNbO3) ridge waveguides. Optical Resonator is one among the most important devices for all tasks described above. LiNbO3 is the substrate commonly used to fabricate optical modulators thanks to its electro-optic characteristics. Since it is produced in high quantity, good quality and large wafers its price is low compared to other electro-optic substrate. We propose to use ion implantation as fabrication technology because in the other way standard optical waveguides realised in LiNbO3 by Proton Exchange (PE) or metal diffusion do not allow small bending radii, which are necessary to keep the circuit footprint small. We will show in fact that this approach allows to fabricate waveguides on Lithium Niobate that are better than PE or metal diffused waveguides as it allows smaller size devices and tailoring of the refractive index profile controlling the implantation parameters. Moreover, we will show that the ridge technology based on enhanced etching rate via ion implantation produces a waveguide with roughness lower than a dry etched one. Finally it has been assessed a complete technological process for fabrication of Microring Resonator devices in Lithium Niobate by ion implantation and the first prototypes have been produced.

Studio preliminare di una rete microcogenerativa con sistema ORC

Studio preliminare di una futura installazione di un banco prova con sistema ORC in parallelo ad una fuel cell. Analisi e scelta dell'impianto ORC, scelta della fonte di calore e del sistema di condensazione in base alle esigenze dell'impianto ORC scelto. Scrittura di un codice di calcolo per simulare l'intero sistema installato.

Deidrogenazione catalitica di idrocarburi per la produzione di H2 "on-board"

Lo studio della deidrogenazione catalitica di idrocarburi affronta uno dei problemi principali per l'applicazione delle fuel cells in aeromobili. La conversione di miscele di idrocarburi in H2 può essere eseguita in loco, evitando le difficoltà di stoccaggio dell'idrogeno: l'H2 prodotto è privo di CO e CO2 e può essere alimentato direttamente alle celle a combustibile per dare energia ai sistemi ausiliari, mentre i prodotti deidrogenati, mantenendo le loro originali caratteristiche possono essere riutilizzati come carburante. In questo un lavoro è stato effettuato uno studio approfondito sulla deidrogenazione parziale (PDH) di diverse miscele di idrocarburi e carburante avio JetA1 desolforato utilizzando Pt-Sn/Al2O3, con l'obiettivo di mettere in luce i principali parametri (condizioni di reazione e composizione di catalizzatore) coinvolti nel processo di deidrogenazione. Inoltre, la PDH di miscele idrocarburiche e di Jet-A1 ha evidenziato che il problema principale in questa reazione è la disattivazione del catalizzatore, a causa della formazione di residui carboniosi e dell’avvelenamento da zolfo. Il meccanismo di disattivazione da residui carboniosi è stato studiato a fondo, essendo uno dei principali fattori che influenzano la vita del catalizzatore e di conseguenza l'applicabilità processo. Alimentando molecole modello separatamente, è stato possibile discriminare le classi di composti che sono coinvolti principalmente nella produzione di H2 o nell’avvelenamento del catalizzatore. Una riduzione parziale della velocità di disattivazione è stata ottenuta modulando l'acidità del catalizzatore al fine di ottimizzare le condizioni di reazione. I catalizzatori Pt-Sn modificati hanno mostrato ottimi risultati in termini di attività, ma soffrono di una disattivazione rapida in presenza di zolfo. Così, la sfida finale di questa ricerca era sviluppare un sistema catalitico in grado di lavorare in condizioni reali con carburante ad alto tenore di zolfo, in questo campo sono stati studiati due nuove classi di materiali: Ni e Co fosfuri supportati su SiO2 e catalizzatori Pd-Pt/Al2O3.

Biogas and bio-hydrogen: production and uses. A review

The first part of this essay aims at investigating the already available and promising technologies for the biogas and bio-hydrogen production from anaerobic digestion of different organic substrates. One strives to show all the peculiarities of this complicate process, such as continuity, number of stages, moisture, biomass preservation and rate of feeding. The main outcome of this part is the awareness of the huge amount of reactor configurations, each of which suitable for a few types of substrate and circumstance. Among the most remarkable results, one may consider first of all the wet continuous stirred tank reactors (CSTR), right to face the high waste production rate in urbanised and industrialised areas. Then, there is the up-flow anaerobic sludge blanket reactor (UASB), aimed at the biomass preservation in case of highly heterogeneous feedstock, which can also be treated in a wise co-digestion scheme. On the other hand, smaller and scattered rural realities can be served by either wet low-rate digesters for homogeneous agricultural by-products (e.g. fixed-dome) or the cheap dry batch reactors for lignocellulose waste and energy crops (e.g. hybrid batch-UASB). The biological and technical aspects raised during the first chapters are later supported with bibliographic research on the important and multifarious large-scale applications the products of the anaerobic digestion may have. After the upgrading techniques, particular care was devoted to their importance as biofuels, highlighting a further and more flexible solution consisting in the reforming to syngas. Then, one shows the electricity generation and the associated heat conversion, stressing on the high potential of fuel cells (FC) as electricity converters. Last but not least, both the use as vehicle fuel and the injection into the gas pipes are considered as promising applications. The consideration of the still important issues of the bio-hydrogen management (e.g. storage and delivery) may lead to the conclusion that it would be far more challenging to implement than bio-methane, which can potentially “inherit” the assets of the similar fossil natural gas. Thanks to the gathered knowledge, one devotes a chapter to the energetic and financial study of a hybrid power system supplied by biogas and made of different pieces of equipment (natural gas thermocatalitic unit, molten carbonate fuel cell and combined-cycle gas turbine structure). A parallel analysis on a bio-methane-fed CCGT system is carried out in order to compare the two solutions. Both studies show that the apparent inconvenience of the hybrid system actually emphasises the importance of extending the computations to a broader reality, i.e. the upstream processes for the biofuel production and the environmental/social drawbacks due to fossil-derived emissions. Thanks to this “boundary widening”, one can realise the hidden benefits of the hybrid over the CCGT system.

Advanced reconstructive technologies for periodontal tissue repair

Reconstructive therapies to promote the regeneration of lost periodontal support have been investigated through both preclinical and clinical studies. Advanced regenerative technologies using new barrier-membrane techniques, cell-growth-stimulating proteins or gene-delivery applications have entered the clinical arena. Wound-healing approaches using growth factors to target the restoration of tooth-supporting bone, periodontal ligament and cementum are shown to significantly advance the field of periodontal-regenerative medicine. Topical delivery of growth factors, such as platelet-derived growth factor, fibroblast growth factor or bone morphogenetic proteins, to periodontal wounds has demonstrated promising results. Future directions in the delivery of growth factors or other signaling models involve the development of innovative scaffolding matrices, cell therapy and gene transfer, and these issues are discussed in this paper.

The Effect of Various Electrode Microstructure Parameters on the Effective Conductivity and Three-Phase Boundary Density of Infiltrated SOFC Electrodes

Solid oxide fuel cell (SOFC) technology has the potential to be a significant player in our future energy technology repertoire based on its ability to convert chemical energy into electrical energy. Infiltrated SOFCs, in particular, have demonstrated improved performance and at lower cost than traditional SOFCs. An infiltrated electrode comprises porous ceramic scaffolding (typically constructed from the oxygen ion conducting material) that is infiltrated with electron conducting and catalytic particles. Two important SOFC electrode properties are effective conductivity and three phase boundary density (TPB). Researchers study these electrode properties separately, and fail to recognize them as competing properties. This thesis aims to (1) develop a method to model the TPB density and use it to determine the effect of porosity, scaffolding particle size, and pore former size on TPB density as well as to (2) compare the effect of porosity, scaffolding particle size, and pore former size on TPB density and effective conductivity to determine a desired set of parameters for infiltrated SOFC electrode performance. A computational model was used to study the effect of microstructure parameters on the effective conductivity and TPB density of the infiltrated SOFC electrode. From this study, effective conductivity and TPB density are determined to be competing properties of SOFC electrodes. Increased porosity, scaffolding particle size, and pore former particle size increase the effective conductivity for a given infiltrate loading above percolation threshold. Increased scaffolding particle size and pore former size ratio, however, decreases the TPB density. The maximum TPB density is achievable between porosities of 45% and 60%. The effect of microstructure parameters are more prominent at low loading with scaffolding particle size being the most significant factor and pore former size ratio being the least significant factor.