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.

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.

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.

Oxygen vacancies as active sites for water dissociation on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy experiments and density functional theory calculations, we determine unambiguously the active surface site responsible for the dissociation of water molecules adsorbed on rutile TiO2(110). Oxygen vacancies in the surface layer are shown to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water is able to diffuse to the active site.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.

Muntatge i caracterització d'una placa DSSC: Buscant potència

Treball de recerca realitzat per alumnes d'ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit científic del Jovent l'any 2009. Els objectius inicials foren la construcció d una 'Cèl•lula Solar Sensibilitzada mitjançant un Colorant’ (DSSC) amb el tint d una col llombarda i posterior caracterització segons el dossier 'Nanocrystalline Solar Cell Kit: Recreating Photosynthesis’. Les DSSC (Dye Sensitized Solar Cell) són un tipus de cèl•lules que imiten els principis que la fotosíntesis ha fet servir exitosament durant més de 3,5 bilions d anys. S’han construït algunes DSSC i se n’ha provat la seva eficiència. El seu funcionament es basa en l’energia d’un fotó que excita un electró i el fa saltar de nivell energètic fins que es desprèn de l’àtom de colorant, deixant un forat en la molècula. Aquest electró lliure passa a través de la capa de TiO2 fins arribar a la càrrega on es genera el corrent elèctric. Tot seguit, l’electró arriba al contra-elèctrode i és aquí on entra en contacte amb l’electròlit, el mediador iode/triiode. Aquest regenera l’electró, que anteriorment ha saltat del colorant, oxidant-se ell mateix.

A Log-linear model of grain size influence on the geochemistry of sediments

Sediment composition is mainly controlled by the nature of the source rock(s), and chemical (weathering) and physical processes (mechanical crushing, abrasion, hydrodynamic sorting) during alteration and transport. Although the factors controlling these processes are conceptually well understood, detailed quantification of compositional changes induced by a single process are rare, as are examples where the effects of several processes can be distinguished. The present study was designed to characterize the role of mechanical crushing and sorting in the absence of chemical weathering. Twenty sediment samples were taken from Alpine glaciers that erode almost pure granitoid lithologies. For each sample, 11 grain-size fractions from granules to clay (ø grades &-1 to &9) were separated, and each fraction was analysed for its chemical composition.The presence of clear steps in the box-plots of all parts (in adequate ilr and clr scales) against ø is assumed to be explained by typical crystal size ranges for the relevant mineral phases. These scatter plots and the biplot suggest a splitting of the full grain size range into three groups: coarser than ø=4 (comparatively rich in SiO2, Na2O, K2O, Al2O3, and dominated by “felsic” minerals like quartz and feldspar), finer than ø=8 (comparatively rich in TiO2, MnO, MgO, Fe2O3, mostly related to “mafic” sheet silicates like biotite and chlorite), and intermediate grains sizes (4≤ø &8; comparatively rich in P2O5 and CaO, related to apatite, some feldspar).To further test the absence of chemical weathering, the observed compositions were regressed against three explanatory variables: a trend on grain size in ø scale, a step function for ø≥4, and another for ø≥8. The original hypothesis was that the trend could be identified with weathering effects, whereas each step function would highlight those minerals with biggest characteristic size at its lower end. Results suggest that this assumption is reasonable for the step function, but that besides weathering some other factors (different mechanical behavior of minerals) have also an important contribution to the trend.Key words: sediment, geochemistry, grain size, regression, step function

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

The Electronic Structure of Co-Sputtered Zinc Indium Tin Oxide Thin Films

Zinc indium tin oxide (ZITO) transparent conductive oxide layers were deposited via radio frequency (RF) magnetron co-sputtering at room temperature. A series of samples with gradually varying zinc content was investigated. The samples were characterized with x-ray and ultraviolet photoemission spectroscopy (XPS, UPS) to determine the electronic structure of the surface. Valence and conduction bands maxima (VBM, CBM), and work function were determined. The experiments indicate that increasing Zn content results in films with a higher defect rate at the surface leading to the formation of a degenerately doped surface layer if the Zn content surpasses 50%. Furthermore, the experiments demonstrate that ZITO is susceptible to ultraviolet light induced work function reduction, similar to what was earlier observed on ITO and TiO2 films.

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS)supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

A Comparison of the Environmental Impact of Different AOPs: Risk Indexes

Today, environmental impact associated with pollution treatment is a matter of great concern. A method is proposed for evaluating environmental risk associated with Advanced Oxidation Processes (AOPs) applied to wastewater treatment. The method is based on the type of pollution (wastewater, solids, air or soil) and on materials and energy consumption. An Environmental Risk Index (E), constructed from numerical criteria provided, is presented for environmental comparison of processes and/or operations. The Operation Environmental Risk Index (EOi) for each of the unit operations involved in the process and the Aspects Environmental Risk Index (EAj) for process conditions were also estimated. Relative indexes were calculated to evaluate the risk of each operation (E/NOP) or aspect (E/NAS) involved in the process, and the percentage of the maximum achievable for each operation and aspect was found. A practical application of the method is presented for two AOPs: photo-Fenton and heterogeneous photocatalysis with suspended TiO2 in Solarbox. The results report the environmental risks associated with each process, so that AOPs tested and the operations involved with them can be compared.