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Direct air capture and integrated conversion is a very attractive strategy to reduce CO2 concentration in the atmosphere. However, the existing capturing processes are technologically challenging due to the costs of the processes and the low concentration of CO2. The efficient valorization of the CO2 captured could help overcome many techno-economic limitations. Here, we present a novel economical methodology for direct air capture and conversion that is able to efficiently convert CO2 from the air into cyclic carbonates. The new approach employs commercially available basic ionic liquids, works without the need for sophisticated and expensive co-catalysts or sorbents and under mild reaction conditions. The CO2 from atmospheric air was efficiently captured by IL solution (0.98 molCO2/molIL) and, subsequently, completely converted into cyclic carbonates using epoxides or halohydrins potentially derived from biomass as substrates. A mechanism of conversion was evaluated, which helped to identify relevant reaction intermediates based on halohydrins, and consequently, a 100% selectivity was obtained using the new methodology.

A combination of thylakoid membranes (TMs) as photobiocatalysts with high-surface-area electroactive materials could hold great potential for sustainable “green” solar energy conversion. We have studied the orientated immobilization of TMs on high-surface-area graphene electrodes, which were fabricated by electroreduction of graphene oxide and simultaneous electrodeposition with further aminoaryl functionalization. We have achieved the highest performance to date under direct electron transfer conditions through a biocompatible “wiring” of TMs to graphene sheets. The photobiocurrent density generated by the optimized mediator-free TM-based bioanodes yielded up to 5.24 ± 0.50 μA cm–2. The photobioelectrochemical cell integrating the photobioanode in combination with an oxygen reducing enzymatic biocathode delivered a maximum power output of 1.79 ± 0.19 μW cm–2. Our approach ensures a simplified cell design, a greater load of photosynthetic units, a minimized overpotential loss, and an enhanced overall performance. The authors thank the following agencies for financial support: the European Commission (”Bioenergy” FP7-PEOPLE-2013-ITN-607793), the Ørsted-COFUND Postdoc fellowship at DTU (Agreement No. 2014-5908), and the Swedish Research Council (project 2014-5908), and Independent Research Fund Denmark-Nature Sciences (DFF-FNU, Project No. DFF-7014-00302). Peer reviewed

We report the energy performance of a new platinum-free alkaline direct formate fuel cell, equipped with a commercial anion exchange membrane, a nanostructured Pd/C anode and a Fe-Co/C cathode. The cell was investigated both at room temperature and at 60 degrees C for the determination of the following parameters: (i) maximum power density, (ii) delivered energy, (iii) faradic (fuel conversion) and energy efficiency. These parameters show a dramatic dependence on fuel composition. The highest energy efficiency is obtained using high energy density fuel (4 M KCOOH and 4 M KOH) and with a maximum operating temperature of 60 degrees C. This represents a key step in the progress of alkaline platinum-free DFFC technology, demonstrating their potential as power sources for portable electronic devices and remote power generation systems. For example, a fuel load of 750 ml in a DFFC device operating at 60 degrees C would be able to produce 90 W h of energy, that required to fully charge the battery of a laptop computer. (C) 2016 Elsevier Ltd. All rights reserved.

This paper presents an overview of the emerging trends in the development of electrical generators for large wind turbines. To describe the developments in the design of electrical generators, it is necessary to look at the conversion system as a whole, and then, the structural and mechanical performances of the drive train need to be considered. Many drive train configurations have been proposed for large wind turbines; they should ensure high reliability, long availability and reduced maintainability. Although most installed wind turbines are geared, directly driven wind turbines with permanent magnet generators have attracted growing interest in the last few years, which has been in parallel to the continuous increase of the per unit turbine power. The aim of this work is to present the recent commercial designs of electrical generators in large wind turbines. Both the strengths and weaknesses of the existing systems are discussed. The most emerging technologies in high-power, low-speed electrical generators are investigated. Furthermore, a comparative analysis of different electrical generator concepts is performed, and the generators are assessed upon a list of criteria such as the mass, cost, and mass-to-torque ratio. Within the framework of these criteria, it may help to determine whether the electrical generator is technically feasible and economically viable for high-power wind turbines. Finally, this review could help to determine suitable generators for use in large and ultra-large wind energy systems.

The bottom-up engineering of nanomaterials using solution-processing strategies is of particular interest for reducing cost and optimizing the performance of TE materials and devices. This thesis focuses on the development of scalable methods for the production of TE nanomaterials with optimized performance. The thesis is divided into 5 chapters. Chapter 1 introduces solution-based approaches for producing functional nanomaterials and the general state of the art in the field of thermoelectricity. Chapter 2 and chapter 3 present a fast and simple molecular ink-based method to produce low cost and crystallographically textured SnSe2 and SnSe nanomaterials. Molecular ink printing techniques could offer a scalable approach to fabricate TE devices on flexible substrates. In these chapters, I proved that cost-effective p-type SnSe NPLs could be produced by a molecular ink-based strategy that allowed introducing controlled amounts of Te to achieve unprecedentedly high TE figure of merit. On the other hand, n-type SnSe2 nanomaterials were also intentionally produced from the same strategy to complement an all Sn-Se based device. Both of the bulk nanomaterials displayed significant crystallographic texture after hot pressing, resulting in highly anisotropic charge and heat transport properties. Different approaches were applied to optimize their TE performance: SnSe2 NPLs were blended with metal NPs to produce a metal-semiconductor NC. The electrical conductivities of the blends were significantly improved with respect to bare SnSe2 bulk nanomaterial and a three-fold increase in the TE figure of merit was obtained, reaching unprecedented values up to ZT = 0.65 for SnSe2 material. For SnSe nanomaterials, I demonstrate that the introduction of small amounts of tellurium in the precursor ink allowed reducing the band gap, increasing both charge carrier concentration and mobility, especially cross plane, with a minimal decrease of the Seebeck coefficient. This strategy translated into record out of plane ZT values at 800 K, ZT=1.05 Chapter 4 and chapter 5 describe two different strategies to produce Bi2Te3-Cu2-xTe NCs based on the consolidation of nanostructured building blocks. I first detail a two-step solution-based process to produce the Bi2Te3-Cu2-xTe heteronanostructures, based on the growth of Cu2-xTe nanocrystals on the surface of Bi2Te3 nanowires. The transport properties of the NCs are investigated as a function of the amount of Cu introduced, which reveal that the presence of Cu decreases the material thermal conductivity through promotion of phonon scattering, modulates the charge carrier concentration through electron spillover, and increases the Seebeck coefficient through filtering of charge carriers at energy barriers. These effects result in an improvement of over 50% of the TE figure of merit of Bi2Te3. As comparison, I produced Bi2Te3-Cu2-xTe NCs by directly mixing proper ratio of individual Bi2Te3 nanowires with Cu2-xTe nanocubes and consolidating the resulting NP mixture by hot-press. A significant difference of transport properties was detected when compared with NCs fabricated by hot-pressing heterostructured Bi2Te3-Cu2-xTe nanowires. On the contrary to the composite obtained from hetero- nanostructures, the presence of Cu2-xTe nanodomains did not lead to a significant reduction of the lattice thermal conductivity of the reference Bi2Te3, which is already very low here, but it resulted in a nearly threefold increase of its power factor. Additionally, the presence of Cu2-xTe resulted in a strong increase of the Seebeck coefficient. This increase is related to the energy filtering of charge carriers at energy barriers within Bi2Te3 domains created by the accumulation of electrons in the regions nearby Cu2-xTe/Bi2Te3 junctions. Overall, a significant improvement of figure of merit, up to a 250%, was obtained with the suitable combination of Cu2-xTe NPs and Bi2Te3 nanowires. Finally, the main conclusions of this thesis and some perspectives for future work are presented. La ingeniería de nanomateriales a partir del procesado en solución es de particular interés para optimizar el rendimiento de los materiales y dispositivos termoeléctricos. . Esta tesis estáse centra en el diseño y el ensamblaje racional de nanomateriales termoeléctricos de alto rendimiento a través de procesado en solución. La tesis se divide en 5 capítulos. El Capítulo 1 aborda la introducción fundamental del enfoque sintético para producir nanomateriales funcionales. Los capítulos 2 y 3 presentan un método rápido y simple basado en soluciones para producir nanomateriales SnSe2 y SnSe con textura cristalográfica. Dado que los calcogenuros de estaño son materiales especialmente interesantes para la conversión de energía termoeléctrica, se sintetizaron nanoplacas SnSe y SnSe2 controlables por forma mediante una estrategia basada en tinta molecular para lograr una figura de mérito termoeléctrica sin precedentes por dopaje con Te/Cu. Ambos nanomateriales mostraron una textura cristalográfica significativa después del prensado en caliente, lo que dio como resultado unas propiedades de transporte de carga calor altamente anisotrópicas. Los capítulos 4 y 5 describen dos estrategias diferentes para producir nanocompuestos Bi2Te3-Cu2-xTe basados en la consolidación de nanoestructuras. La presencia de Cu2-xTe da como resultado un fuerte aumento del coeficiente de Seebeck. Este aumento está relacionado con el filtrado de los portadores de carga en función de su energía en las barreras de energía dentro de los dominios Bi2Te3 creados por la acumulación de electrones en las regiones cercanas a las uniones Cu2-xTe / Bi2Te3. En general, se obtiene una mejora significativa de la figura de mérito con nanocompuestos Bi2Te3-Cu2-xTe. Finalmente, en el último capítulo se presentan las principales conclusiones de esta tesis y algunas perspectivas para trabajos futuros.

In this thesis, it is detailed the bottom-up production and characterization of thermoelectric (TE) nanomaterials with significant enhanced performance by using colloidal nanocrystals (NCs) as building blocks. The production of TE nanomaterials with significant improved figure of merit (ZT), has to do, not only with the precise control of the NCs properties, but also with the further fine control over the crystallographic alignment of nanograins of highly anisotropic materials. The first part of the thesis correspond to the study of synthetic routes to produce high quality chalcogenide NCs that are doped during the NC synthesis, in order to control the charge carrier concentration. The system studied was I−V−VI chalcogenide semiconductor, specifically it was produced the materials: AgSbSe2 and Cu3SbSe4. A low-cost, high-yield and scalable synthesis route to produce monodisperse of AgSbSe2 and Cu3SbSe4 NCs was obtained. After ligand displacement, the NCs were used as building blocks to produce TE nanomaterials. Additionally, by means of substitutional doping, a large increment in the power factor and relatively lower thermal conductivities were observed. The optimization of the doping concentration resulted in ZT values of 1.10 at 640 K for AgSb0.98Bi0.02Se2, and of 1.26 at 673 K for Cu3Sb0.88Sn0.10Bi0.02Se4, which represents a significant increase beyond the state of the art in Te-free multinary Ag/Cu-based chalcogenide materials. In the second part of the thesis, the work about PbS-metal (Cu and Sn) nanocomposites produced by blending procedure is presented. The low work function metal is able to inject electrons to the intrinsic PbS matrix, which is another strategy to control the charge carrier concentration. The power factor is dramatically enhanced due to the increase of the electrical conductivity in the nanocomposites. Consequently, the ZTmax was remarkably enhanced by two times as compared with the pristine PbS. Furthermore, we also compared the TE performance of microcrystalline composites with the same composition as in nanocrystalline composites; commercial PbS host with Cu particles. The results revealed that with the same metal addition, higher electrical conductivities were obtained in the nanocomposite, but higher Seebeck coefficients were maintained in the microcomposite. Moreover, higher thermal conductivities were also obtained in the microcomposite. Finally, the figure of merit ZT were higher for the microcomposite system in the low temperature range, but much lower in the higher temperature range compared with the nanocomposites system. In the last block, the process of production of crystallographically textured materials is presented. We face here the challenge of bottom-up approaches to control the crystallographic alignment of nanograins. The production of nanostructured Bi2Te3-based alloys is presented. This can be done with controlled stoichiometry by solution-processing, and crystallographic texture by liquid-phase sintering using multiple pressure and release steps at 480 °C, above the tellurium melting point. Additionally, we explain the possible mechanism to produce the highly textured nanomaterials. This strategy results in record TE figures of merit: ZT=1.83 at 420 K for Bi0.5Sb2.5Te3 and ZT=1.31 for Bi2Te2.7Se0.3 at 440 K when averaged over 5 materials in the c direction, respectively. These high figures of merit extended over a wide temperature range, which results in energy conversion efficiencies a 50% higher than commercial ingots in the similar temperature range. In summary, different strategies to improve the TE performance of bulk nanostructured materials produced by bottom-up engineering of NCs, have been studied and confirmed in this thesis. Additionally, it has been proven that the solution-processed synthesis approach is low-cost, compatible with the scale-up engineering, and also versatile in tuning the size, shape, composition, and microstructure, among others parameters of different nanomaterials to optimize their TE properties. Los nanocristales (NCs) coloidales tienen excelentes propiedades para diferentes aplicaciones, como la conversión de energía, la catálisis, los dispositivos electrónicos y optoelectrónicos, entre otros. Así mismo, la síntesis coloidal de NCs tiene ventajas en el control del tamaño, forma y composición a nivel de la nanoescala; las bajas temperaturas de reacción; y la no necesidad de equipos especializados. Este proyecto se concentra en el diseño racional y la ingeniería de materiales termoeléctricos (TE) nanoestructurados de alta eficiencia, usando la estrategia del ensamblado ascendente (bottom-up) de NCs coloidales. Primero, se diseñó una ruta de síntesis de bajo costo, alto rendimiento, con la cual, se obtuvieron NCs de AgSbSe2 y Cu3SbSe4. La optimización de la concentración de dopaje resultó en valores para la figura de mérito TE, ZT, de 1.10 a 640 K para AgSb0.98Bi0.02Se2, y de 1.26 at 673 K para Cu3Sb0.88Sn0.10Bi0.02Se4. El material con mejores propiedades se usó para la producción de un generador TE en forma de anillo, para acoplarlo a los tubos de escape de gases, obteniendo una potencia eléctrica de 1mW por elemento TE con una diferencia de temperatura de 160 °C. En la segunda parte, se presenta el trabajo de la producción de nanocopuestos de PbS-metal (Cu y Sn) usando un procedimiento versátil de mezcla de NCs. La función de trabajo del metal es capaz de inyectar electrones a la matriz intrínseca de PbS. El factor de potencia TE, se ve dramáticamente incrementado debido al aumento en la conductividad eléctrica en los nanocompuestos TE. Consecuentemente, el valor máximo de ZT se vio excepcionalmente incrementado por el doble del valor comparado con el material original PbS. Finalmente, se presenta el proceso de producción de materiales texturizados cristalográficamente, produciendo materiales tipo p BixSb2-xTe3 y tipo n Bi2Te3-xSex. Se controló la estequiometria durante el procesamiento en solución y la textura cristalográfica, por medio de la sinterización en fase líquida con un procedimiento de múltiples pasos de presión y relajación a una temperatura de 480°C. Los valores de la figura de mérito TE presentan el record de: ZT=1.83 a 420 K para Bi0.5Sb2.5Te3 y ZT=1.31 para Bi2Te2.7Se0.3 a 440 K.

This article presents the demonstrative development of the Towards Intelligent DC-based hybrid Grids Optimizing the Network performance (TIGON) project at the Centre for the Development of Renewable Energy - Centre for Energy, Environmental and Technological Research (CE.D.E.R.-CIEMAT), as well as the established objectives to be achieved with the implementation of a microgrid with smart grid architecture based on direct current (DC) and integrated into the current energy system. This type of architecture is proposed as a future solution to reduce energy losses caused by DC-alternating current (AC) conversions, increasing the overall performance and profitability of hybrid grids. All this without forgetting to ensure the supply, stability and reliability of the system with the development of all the necessary equipment and protections to make this approach a reality. The microgrid design and process of implementation start from a transformation centre, from which the medium voltage direct current (MVDC) grid will be created by the Solid State Transformer (SST). In the MVDC grid, we will find a bank of lead-acid batteries and other essential equipment in the microgrid, a DC/DC converter that will create the low voltage direct current (LVDC) grid. On the LVDC side, several branches have been designed to connect the rest of the systems; generation (mini-wind and photovoltaic), storage (LFP batteries) and loads (AC and DC loads). Each of the equipment will have a connection to the DC grid through converters made exclusively for this equipment and connexion to the AC grid, which will allow us to obtain all the necessary data to carry out the required studies to achieve the established objectives of the project.

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.