Síntesi de nanopartícules de TiO2 fàcilment processables i el seu ús per a fabricar a baixa temperatura cel·les solars sensibilitzades

La gran demanda energètica i la problemàtica dels combustibles fòssils i d‟altres recursos per a obtenir energia posen de manifest la necessitat de desenvolupar tecnologies netes, sostenibles i econòmicament viables de generació d‟energia. En aquest àmbit, les cel·les solars sensibilitzades amb colorant (Dye Sensitized Solar Cells, DSSC), que transformen l‟energia solar a energia elèctrica, són una solució factible. A més, el desenvolupament de mètodes per a construir aquestes cel·les a baixa temperatura permetria fabricar-les sobre substrats plàstics, fet que els donaria un valor afegit i permetria una producció en continu, ràpida i amb baix cost tant, econòmic, com d‟impacte ambiental. Aquest treball presenta el desenvolupament d‟un mètode de producció a baixa temperatura (140 ºC) de DSSC, amb eficiència de 5,9 % sobre substrats FTO/vidre. Aquest valor és superior a la majoria de les eficiències reportades a la bibliografia de DSSC construïdes a baixa temperatura. Les capes mesoporoses que formen els elèctrodes de les DCCS es dipositen per doctor blade a partir d‟una pasta composta per nanopartícules de TiO2, de 4-8 nm, recobertes d‟àcid 3,6,9-trioxadecanoic, per nanopartícules de Degussa P25, de 20-25 nm, i com a dissolvents només s‟utilitza aigua i etanol. L‟aplicació d‟un tractament a 140 ºC permet eliminar la matèria orgànica de la superfície de les nanopartícules de 4-8 nm i unir-les a les de Degussa P25. Aquest fet permet obtenir capes mesoporoses sinteritzades de 6 μm de gruix. A més, l‟aplicació d‟un post-tractament, en el qual s‟utilitza l‟àcid hexafluoro titànic (IV), produeix un lleuger increment en l‟eficiència. Endemés, l‟obtenció de capes primes de TiO2 sobre substrats plàstics és un tema d‟actualitat a causa de la falta de mètodes de deposició a baixa temperatura. En aquest context, s‟ha sintetitzat, mitjançant processos respectuosos amb el medi ambient nanopartícules de TiO2 cristal·lí modificades superficialment amb lauril gal·lat i àcid 3,6,9-trioxodecanoic. Les nanopartícules poden ser dispersades en dissolvents orgànics i aigua respectivament, fet que permet obtenir suspensions estables i de fàcil manipulació. Aquestes poden ser utilitzades com a precursores per a obtenir capes primes a baixa temperatura de TiO2 cristal·lí. En concret, les capes primes formades per nanopartícules de TiO2 modificades amb àcid 3,6,9-trioxodecanoic s‟han utilitzat com a blocking layer en les DSSC construïdes a baixa temperatura.

Uso de TiO2 dopado con nitrógeno para la generación de hidrógeno bajo irradiación con luz visible

Se desarrollaron catalizadores de TiO2 dopados con nitrógeno para conseguir actividad fotocatalítica bajo irradiación visible. En este trabajo se reporta la síntesis de TiO2-N, usando urea y nitrato de amonio (NH4NO3) como precursores de nitrógeno, tanto a partir de un TiO2 generado in situ (método sol-gel) como mediante la modificación de un TiO2 comercial. Así mismo, se varió la concentración de urea para encontrar el valor óptimo de nitrógeno, lo cual se comprobó mediante la oxidación fotocatalítica de ácido oxálico bajo irradiación con luz visible. Los materiales sintetizados se caracterizaron por medio de análisis elemental, y por reflectancia difusa UV-visible, encontrándose nitrógeno en todas las muestras, y un valor del ancho de banda prohibida en el rango 2-2,8 eV. Lamentablemente, se detectó una pérdida de nitrógeno cuando los fotocatalizadores eran reutilizados, lo cual causó una disminución de su actividad después de cada reacción, ya sea en presencia de oxígeno, o en ausencia de éste mientras se generaba hidrógeno. Entre los dopantes investigados el NH4NO3 mostro una mejor eficiencia en la producción de hidrógeno. Además, los resultados experimentales revelaron claramente que la deposición de platino en la superficie de los catalizadores TiO2-N desempeña un papel fundamental en el aumento de la generación de hidrógeno. Sin embargo, esta mejora dependía claramente del método de preparación de las muestras, obteniéndose mejores resultados con el TiO2-p25.

Síntesis, caracterización y ensayos cinéticos del nanocomposite RuO2/TiO2/MWCNT/Pt en la producción fotocatalítica de combustibles solares bajo iluminación UV y VIS

Se prepararon partículas de nanocomposites basados en TiO2 y nanotubos de carbono multicapa platinizados para la obtención de combustibles solares. Se evaluó la actividad fotocatalítica del material en la producción de hidrógeno, en procesos de degradación de ácido fórmico, y en la obtención de hidrocarburos a partir de la reducción de CO2 en agua. Los nanocomposites fueron sintetizados por medio de la técnica sol-gel. Se estudió el efecto de la proporción y el diámetro de los nanotubos de carbono en la actividad del material bajo iluminación ultravioleta y visible. Se estudió el efecto de la adición de RuO2 (0,5% wt.) en la actividad bajo iluminación visible. Los materiales fueron caracterizados por ATR, XRD, BET, HRTEM y SEM. Se obtuvieron sólidos macroporosos, con contenido de fase anatasa superior al 99% y tamaño cristalino comprendido entre 15 y 21 nm. Los resultados cinéticos mostraron una producción óptima de hidrógeno para el composite TiO2/(5wt.%)MWCNT/Pt(60-80 nm), con eficiencia cuántica y eficiencia energética de 1,27% y 0,27%, respectivamente. En el caso de radiación visible, la producción de hidrógeno fue nula para los composites TiO2/MWCNT/Pt, mientras que para el sistema RuO2/TiO2/MWCNT/Pt se observó que la adicción de MWCNT inhibía la actividad fotocatalítica del composite RuO2/TiO2 en la región del visible. Por otra parte, en los ensayos de reducción de CO2 no se detectó ningún producto de reacción.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Avoiding sensor blindness in Geiger mode avalanche photodiode arrays fabricated in a conventional CMOS process

The need to move forward in the knowledge of the subatomic world has stimulated the development of new particle colliders. However, the objectives of the next generation of colliders sets unprecedented challenges to the detector performance. The purpose of this contribution is to present a bidimensional array based on avalanche photodiodes operated in the Geiger mode to track high energy particles in future linear colliders. The bidimensional array can function in a gated mode to reduce the probability to detect noise counts interfering with real events. Low reverse overvoltages are used to lessen the dark count rate. Experimental results demonstrate that the prototype fabricated with a standard HV-CMOS process presents an increased efficiency and avoids sensor blindness by applying the proposed techniques.

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

On-line event detection by recursive dynamic principal component analysis and gas sensor arrays under drift conditions

Leakage detection is an important issue in many chemical sensing applications. Leakage detection hy thresholds suffers from important drawbacks when sensors have serious drifts or they are affected by cross-sensitivities. Here we present an adaptive method based in a Dynamic Principal Component Analysis that models the relationships between the sensors in the may. In normal conditions a certain variance distribution characterizes sensor signals. However, in the presence of a new source of variance the PCA decomposition changes drastically. In order to prevent the influence of sensor drifts the model is adaptive and it is calculated in a recursive manner with minimum computational effort. The behavior of this technique is studied with synthetic signals and with real signals arising by oil vapor leakages in an air compressor. Results clearly demonstrate the efficiency of the proposed method.

Nonlinear inverse dynamic models of gas sensing systems based on chemical sensor arrays for quantitative measurements

Gas sensing systems based on low-cost chemical sensor arrays are gaining interest for the analysis of multicomponent gas mixtures. These sensors show different problems, e.g., nonlinearities and slow time-response, which can be partially solved by digital signal processing. Our approach is based on building a nonlinear inverse dynamic system. Results for different identification techniques, including artificial neural networks and Wiener series, are compared in terms of measurement accuracy.

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.

Competitive evaporation in arrays of droplets

We consider the evaporation of periodic arrays of initially equal droplets in two-dimensional systems with open (absorbing) boundaries. Our study is based on the numerical solution of the Cahn-Hilliard equation. We show that due to cooperative effects the droplets which are further from the boundary may evaporate earlier than those in the boundary¿s vicinity. The time evolution of the overall amount of matter in the system is also studied.

Pulse propagation sustained by noise in arrays of bistable electronic circuits

One-dimensional arrays of nonlinear electronic circuits are shown to support propagation of pulses when operating in a locally bistable regime, provided the circuits are under the influence of a global noise. These external random fluctuations are applied to the parameter that controls the transition between bistable and monostable dynamics in the individual circuits. As a result, propagating fronts become destabilized in the presence of noise, and the system self-organizes to allow the transmission of pulses. The phenomenon is also observed in weakly coupled arrays, when propagation failure arises in the absence of noise.

Synthesis, structural order and magnetic behavior of self-assembled epsilon-Co nanocrystal arrays

The synthesis of magnetic nanoparticles with monodispere size distributions, their self assembly into ordered arrays and their magnetic behavior as a function of structural order (ferrofluids and 2D assemblies) are presented. Magnetic colloids of monodispersed, passivated, cobalt nanocrystals were produced by the rapid pyrolysis of cobalt carbonyl in solution. The size, size distribution (std. dev.< 5%) and the shape of the nanocrystals were controlled by varying the surfactant, its concentration, the reaction rate and the reaction temperature. The Co particles are defect-free single crystals with a complex cubic structure related to the beta phase of manganese (epsilon-Co). In the 2D assembly, a collective behavior was observed in the low-field susceptibility measurements where the magnetization of the zero field cooled process increases steadily and the magnetization of the field cooling process is independent the temperature. This was different from the observed behavior in a sample comprised of disordered interacting particles. A strong paramagnetic contribution appears at very low temperatures where the magnetization increases drastically after field cooling the sample. This has been attributed to the Co surfactant-particle interface since no magnetic atomic impurities are present in these samples.

Competitive evaporation in arrays of droplets

We consider the evaporation of periodic arrays of initially equal droplets in two-dimensional systems with open (absorbing) boundaries. Our study is based on the numerical solution of the Cahn-Hilliard equation. We show that due to cooperative effects the droplets which are further from the boundary may evaporate earlier than those in the boundary¿s vicinity. The time evolution of the overall amount of matter in the system is also studied.

Enhanced pulse propagation in non-linear arrays of oscillators

The propagation of a pulse in a nonlinear array of oscillators is influenced by the nature of the array and by its coupling to a thermal environment. For example, in some arrays a pulse can be speeded up while in others a pulse can be slowed down by raising the temperature. We begin by showing that an energy pulse (one dimension) or energy front (two dimensions) travels more rapidly and remains more localized over greater distances in an isolated array (microcanonical) of hard springs than in a harmonic array or in a soft-springed array. Increasing the pulse amplitude causes it to speed up in a hard chain, leaves the pulse speed unchanged in a harmonic system, and slows down the pulse in a soft chain. Connection of each site to a thermal environment (canonical) affects these results very differently in each type of array. In a hard chain the dissipative forces slow down the pulse while raising the temperature speeds it up. In a soft chain the opposite occurs: the dissipative forces actually speed up the pulse, while raising the temperature slows it down. In a harmonic chain neither dissipation nor temperature changes affect the pulse speed. These and other results are explained on the basis of the frequency vs energy relations in the various arrays