Optimization of the large scale synthesis of the LSF-20 cathode material for SOFCs

Póster presentado en: 21st World Hydrogen Energy Conference 2016. Zaragoza, Spain. 13-16th June, 2016

Applications of Photoinduced Electron Transfer Chemistry: Photoremovable Protecting Groups and Carbon Dioxide Conversion

Traditional organic chemistry has long been dominated by ground state thermal reactions. The alternative to this is excited state chemistry, which uses light to drive chemical transformations. There is considerable interest in using this clean renewable energy source due to concerns surrounding the combustion byproducts associated with the consumption of fossil fuels. The work presented in this text will focus on the use of light (both ultraviolet and visible) for the following quantitative chemical transformations: (1) the release of compounds containing carboxylic acid and alcohol functional groups and (2) the conversion of carbon dioxide into other useable chemicals. Chapters 1-3 will introduce and explore the use of photoremovable protecting groups (PPGs) for the spatiotemporal control of molecular concentrations. Two new PPGs are discussed, the 2,2,2-tribromoethoxy group for the protection of carboxylic acids and the 9-phenyl-9-tritylone group for the protection of alcohols. Fundamental interest in the factors that affect C–X bond breaking has driven the work presented in this text for the release of carboxylic acid substrates. Product analysis from the UV photolysis of 2,2,2-tribromoethyl-(2′-phenylacetate) in various solvents results in the formation of H–atom abstraction products as well as the release of phenylacetic acid. The deprotection of alcohols is realized through the use of UV or visible light photolysis of 9-phenyl-9-tritylone ethers. Central to this study is the use of photoinduced electron transfer chemistry for the generation of ion diradicals capable of undergoing bond-breaking chemistry leading to the release of the alcohol substrates. Chapters 4 and 5 will explore the use of N-heterocyclic carbenes (NHCs) as a catalyst for the photochemical reduction of carbon dioxide. Previous experiments have demonstrated that NHCs can add to CO2 to form stable zwitterionic species known as N-heterocylic-2-carboxylates (NHC–CO2). Work presented in this text illustrate that the stability of these species is highly dependent on solvent polarity, consistent with a lengthening of the imidazolium to carbon dioxide bond (CNHC–CCO2). Furthermore, these adducts interact with excited state electron donors resulting in the generation of ion diradicals capable of converting carbon dioxide into formic acid.

Exergy analysis of a solar photovoltaic module

PV energy is the direct conversion of solar radiation into electricity. In this paper, an analysis of the influence of parameters such as global irradiance or temperature in the performance of a PV installation has been carried out. A PV module was installed in a building at the University of Málaga, and these parameters were experimentally determined for different days and different conditions of irradiance and temperature. Moreover, IV curves were obtained under these conditions to know the open-circuit voltage and the short-circuit current of the module. With this information, and using the first law of thermodynamics, an energy analysis was performed to determine the energy efficiency of the installation. Similarly, using the second law of thermodynamics, an exergy analysis is used to obtain the exergy efficiency. The results show that the energy efficiency varies between 10% and 12% and the exergy efficiency between 14% and 17%. It was concluded that the exergy analysis is more suitable for studying the performance, and that only electric exergy must be considered as useful exergy. This exergy efficiency can be improved if heat is removed from the PV module surface, and an optimal temperature is reached.

Direct experimental evidence for a multiparticle-hole ground state configuration of deformed Mg-33

The first direct experimental evidence of a multiparticle-hole ground state configuration of the neutron-rich Mg-33 isotope has been obtained via intermediate energy (400 A MeV) Coulomb dissociation measurement. The major part similar to(70 +/- 13)% of the cross section is observed to populate the excited states of Mg-32 after the Coulomb breakup of Mg-33. The shapes of the differential Coulomb dissociation cross sections in coincidence with different core excited states favor that the valence neutron occupies both the s(1/2) and p(3/2) orbitals. These experimental findings suggest a significant reduction and merging of sd-pf shell gaps at N similar to 20 and 28. The ground state configuration of Mg-33 is predominantly a combination of Mg-32(3.0,3.5MeV; 2(-), 1(-)) circle times nu(s1/2), Mg-32(2.5MeV; 2(+)) circle times nu(p3/2), and Mg-32(0; 0(+)) circle times nu(p3/2). The experimentally obtained quantitative spectroscopic information for the valence neutron occupation of the s and p orbitals, coupled with different core states, is in agreement with Monte Carlo shell model (MCSM) calculation using 3 MeV as the shell gap at N = 20.

Whole-body cortisol increases after direct and visual contact with a predator in zebrafish, Danio rerio

Ornamental fish may be severely affected by a stressful environment. Stressors impair the immune response, reproduction and growth rate; thus, the identification of possible stressors will aid to improve the overall quality of ornamental fish. The aim of this study was to determine whole-body cortisol of adult zebrafish, Danio rerio, following visual or direct contact with a predator species. Zebrafish were distributed in three groups: the first group, which consisted of zebrafish reared completely isolated of the predator, was considered the negative control; the second group, in which the predator, Parachromis managuensis was stocked together with zebrafish, was considered the positive control; the third group consisted of zebrafish stocked in a glass aquarium, with direct visual contact with the predator. The mean whole-body cortisol concentration in zebrafish from the negative control was 6.78 +/- 1.12 ng g(-1), a concentration statistically lower than that found in zebrafish having visual contact with the predator (9.26 +/- 0.88 ng g(-1)) which, in turn, was statistically lower than the mean whole-body cortisol of the positive control group (12.35 +/- 1.59 ng g(-1)). The higher whole-body cortisol concentration found in fish from the positive control can be attributed to the detection, by the zebrafish, of relevant risk situations that may involve a combination of chemical, olfactory and visual cues. One of the functions of elevated cortisol is to mobilize energy from body resources to cope with stress. The elevation of whole-body cortisol in fish subjected to visual contact with the predator involves only the visual cue in the recognition of predation risk. We hypothesized that the zebrafish could recognize predator characteristics in P managuensis, such as length, shape, color and behavior. Nonetheless, the elevation of whole-body cortisol in zebrafish suggested that the visual contact of the predator may elicit a stress response in prey fish. This assertion has a strong practical application concerning the species distribution in ornamental fish markets in which prey species should not be allowed to see predator species. Minimizing visual contact between prey and predator fish may improve the quality, viability and welfare of small fish in ornamental fish markets. (c) 2007 Elsevier B.V. All rights reserved.

Understanding Co-translational Protein Targeting and Lithium Dendrite Formation through Free Energy Simulations and Coarse-Grained Models

We describe the application of alchemical free energy methods and coarse-grained models to study two key problems: (i) co-translational protein targeting and insertion to direct membrane proteins to the endoplasmic reticulum for proper localization and folding, (ii) lithium dendrite formation during recharging of lithium metal batteries. We show that conformational changes in the signal recognition particle, a central component of the protein targeting machinery, confer additional specificity during the the recognition of signal sequences. We then develop a three-dimensional coarse-grained model to study the long-timescale dynamics of membrane protein integration at the translocon and a framework for the calculation of binding free energies between the ribosome and translocon. Finally, we develop a coarse-grained model to capture the dynamics of lithium deposition and dissolution at the electrode interface with time-dependent voltages to show that pulse plating and reverse pulse plating methods can mitigate dendrite growth.

Sustainable Energy Production in the United States: Life Cycle Assessment of Biofuels and Bioenergy

The United States of America is making great efforts to transform the renewable and abundant biomass resources into cost-competitive, high-performance biofuels, bioproducts, and biopower. This is the key to increase domestic production of transportation fuels and renewable energy, and reduce greenhouse gas and other pollutant emissions. This dissertation focuses specifically on assessing the life cycle environmental impacts of biofuels and bioenergy produced from renewable feedstocks, such as lignocellulosic biomass, renewable oils and fats. The first part of the dissertation presents the life cycle greenhouse gas (GHG) emissions and energy demands of renewable diesel (RD) and hydroprocessed jet fuels (HRJ). The feedstocks include soybean, camelina, field pennycress, jatropha, algae, tallow and etc. Results show that RD and HRJ produced from these feedstocks reduce GHG emissions by over 50% compared to comparably performing petroleum fuels. Fossil energy requirements are also significantly reduced. The second part of this dissertation discusses the life cycle GHG emissions, energy demands and other environmental aspects of pyrolysis oil as well as pyrolysis oil derived biofuels and bioenergy. The feedstocks include waste materials such as sawmill residues, logging residues, sugarcane bagasse and corn stover, and short rotation forestry feedstocks such as hybrid poplar and willow. These LCA results show that as much as 98% GHG emission savings is possible relative to a petroleum heavy fuel oil. Life cycle GHG savings of 77 to 99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion for electricity, depending on the biomass feedstock and combustion technologies used. Transportation fuels hydroprocessed from pyrolysis oil show over 60% of GHG reductions compared to petroleum gasoline and diesel. The energy required to produce pyrolysis oil and pyrolysis oil derived biofuels and bioelectricity are mainly from renewable biomass, as opposed to fossil energy. Other environmental benefits include human health, ecosystem quality and fossil resources. The third part of the dissertation addresses the direct land use change (dLUC) impact of forest based biofuels and bioenergy. An intensive harvest of aspen in Michigan is investigated to understand the GHG mitigation with biofuels and bioenergy production. The study shows that the intensive harvest of aspen in MI compared to business as usual (BAU) harvesting can produce 18.5 billion gallons of ethanol to blend with gasoline for the transport sector over the next 250 years, or 32.2 billion gallons of bio-oil by the fast pyrolysis process, which can be combusted to generate electricity or upgraded to gasoline and diesel. Intensive harvesting of these forests can result in carbon loss initially in the aspen forest, but eventually accumulates more carbon in the ecosystem, which translates to a CO2 credit from the dLUC impact. Time required for the forest-based biofuels to reach carbon neutrality is approximately 60 years. The last part of the dissertation describes the use of depolymerization model as a tool to understand the kinetic behavior of hemicellulose hydrolysis under dilute acid conditions. Experiments are carried out to measure the concentrations of xylose and xylooligomers during dilute acid hydrolysis of aspen. The experiment data are used to fine tune the parameters of the depolymerization model. The results show that the depolymerization model successfully predicts the xylose monomer profile in the reaction, however, it overestimates the concentrations of xylooligomers.

Applications of advanced and dual energy computed tomography in proton therapy

This thesis focuses on advanced reconstruction methods and Dual Energy (DE) Computed Tomography (CT) applications for proton therapy, aiming at improving patient positioning and investigating approaches to deal with metal artifacts. To tackle the first goal, an algorithm for post-processing input DE images has been developed. The outputs are tumor- and bone-canceled images, which help in recognising structures in patient body. We proved that positioning error is substantially reduced using contrast enhanced images, thus suggesting the potential of such application. If positioning plays a key role in the delivery, even more important is the quality of planning CT. For that, modern CT scanners offer possibility to tackle challenging cases, like treatment of tumors close to metal implants. Possible approaches for dealing with artifacts introduced by such rods have been investigated experimentally at Paul Scherrer Institut (Switzerland), simulating several treatment plans on an anthropomorphic phantom. In particular, we examined the cases in which none, manual or Iterative Metal Artifact Reduction (iMAR) algorithm were used to correct the artifacts, using both Filtered Back Projection and Sinogram Affirmed Iterative Reconstruction as image reconstruction techniques. Moreover, direct stopping power calculation from DE images with iMAR has also been considered as alternative approach. Delivered dose measured with Gafchromic EBT3 films was compared with the one calculated in Treatment Planning System. Residual positioning errors, daily machine dependent uncertainties and film quenching have been taken into account in the analyses. Although plans with multiple fields seemed more robust than single field, results showed in general better agreement between prescribed and delivered dose when using iMAR, especially if combined with DE approach. Thus, we proved the potential of these advanced algorithms in improving dosimetry for plans in presence of metal implants.

An empirical investigation of the impact of global energy transition on Nigerian oil and gas exports

18 months embargo on the thesis and check appendix for copy right materials

Locating the maximum power point for thermoelectric generators for constant heat operation

Thermoelectric generators (TEGs) are solid-state devices that can be used for the direct conversion between heat and electricity. These devices are an attractive option for generating clean energy from heat. There are two modes of operation for TEGs; constant heat and constant temperature. It is a well-known fact that for constant temperature operation, TEGs have a maximum power point lying at half the open circuit voltage of the TEG, for a particular temperature. This work aimed to investigate the position of the maximum power point for Bismuth Telluride TEGs working under constant heat conditions i.e. the heat supply to the TEG is fixed however the temperature across the TEG can vary depending upon its operating conditions. It was found that for constant heat operation, the maximum power point for a TEG is greater than half the open circuit voltage of the TEG.

DNI Measurements in the South of Portugal: Long Term Results through Direct Comparison with Global and Diffuse Radiation Measurements and Existing Time Series

The present work describes the measurement effort for direct normal irradiance (DNI) evaluation in the sunny south of Portugal, with a network of eight radiation measurement stations in several locations (including Évora) providing a good coverage of the region. This new initiative for DNI measurement will still need many years (typically 10 or more) to produce a time series which can claim having long term statistical value. This problem can, however, be temporarily mitigated by measuring DNI at the same time as GHI and DHI, in a place where long term series dating back, already exist for those two. It so happens that a long term series (20 years) of global and diffuse solar irradiation exists for the location Évora. So the expectation is to establish correlations with the goal of attributing at least some long term statistical significance to the short and recent DNI series. The paper describes the setup of the measuring stations and presents the preliminary measurements obtained. It further presents the first correlations of monthly averages between normal beam (DNI), global and diffuse radiation. It then uses these correlations, admittedly without acceptable statistical significance (short series of less than one year of measured data), to exemplify how to get a prediction of long term DNI for Évora. This preliminary obtained value is compared to that predicted by the commercial data from Meteonorm.

Direct nitrous oxide (N2O) fluxes from soils under different land use in Brazil: a critical review.

Brazil typifies the land use changes happening in South America, where natural vegetation is continuously converted into agriculturally used lands, such as cattle pastures and croplands. Such changes in land use are always associated with changes in the soil nutrient cycles and result in altered greenhouse gas fluxes from the soil to the atmosphere. In this study, we analyzed literature values to extract patterns of direct nitrous oxide (N2O) emissions from soils of different ecosystems in Brazil. Fluxes from natural ecosystems exhibited a wide range: whereas median annual flux rates were highest in Amazonian and Atlantic rainforests (2.42 and 0.88 kg N ha-1), emissions from cerrado soils were close to zero. The decrease in emissions from pastures with increasing time after conversion was associated with pasture degradation. We found comparatively low N2O-N fluxes from croplands (-0.07 to 4.26 kg N ha-1 yr-1 , median 0.80 kg N ha-1 yr-1) and a low response to N fertilization. Contrary to the assumptions, soil parameters, such as pH, Corg, and clay content emerged as poor predictors for N2O fluxes. This could be a result of the formation of micro-aggregates, which strongly affect the hydraulic properties of the soil, and consequently define nitrification and denitrification potentials. Since data from croplands mainly derived from areas that had been under natural cerrado vegetation before, it could explain the low emissions under agriculture. Measurements must be more frequent and regionally spread in order to enable sound national estimates.