Effect of niobium dopant on fatigue characteristics of BiFeO3 thin films grown on Pt electrodes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of scandium on the structural and photocatalytic properties of titanium dioxide thin films

Pure and scandium doped-TiO2 thin films were prepared by the sol-gel process and coated by dip coating. The effects of scandium on the phase formation, optical properties and photoactivity of the TiO2 thin films were investigated. The lattice parameters and the crystallinity of the anatase phase, characterized by the Rietveld method, demonstrated that scandium doping affected the structural parameters and crystallinity of the films, modifying the absorption edge. A direct correlation was found between band gap energy and photodegradation efficiency, with lower values of band gap energy augmenting this efficiency. Moreover, a significant improvement in the catalyst's photodegradation efficiency was attained with a scandium concentration of 5.0 mol%. © 2007 Springer Science+Business Media, LLC.

Síntese hidrotérmica de nanopartículas de 'TI''O IND.2', de nanocompósitos metal/'TI''O IND.2' e degradação oxidativa de 4-clorofenol em reator membranar fotocatalítico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Filmes finos de LaNiO3 e PZT preparados pelo métodos das soluções precursoras poliméricas e depositados em substratos de silício

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of the iron doping on the thermal decomposition of the polymeric precursor for the titanium dioxide powder synthesis

The Polymeric Precursor Method has proved suitable for synthesizing reactive powders using low temperatures of calcination, especially when compared with conventional methods. However, during the thermal decomposition of the polymeric precursor the combustion event can be releases an additional heat that raises the temperature of the sample in several tens of degrees Celsius above the set temperature of the oven. This event may be detrimental to some material types, such as the titanium dioxide semiconductor. This ceramic material has a phase transition at around 600 ° C, which involves the irreversible structural rearrangement, characterized by the phase transition from anatase to rutile TiO2 phase. The control of the calcination step then becomes very important because the efficiency of the photocatalyst is dependent on the amount of anatase phase in the material. Furthermore, use of dopant in the material aims to improve various properties, such as increasing the absorption of radiation and in the time of the excited state, shifting of the absorption edge to the visible region, and increasing of the thermal stability of anatase. In this work, samples of titanium dioxide were synthesized by the Polymeric Precursor Method in order to investigate the effect of Fe (III) doping on the calcination stages. Thermal analysis has demonstrated that the Fe (III) insertion at 1 mol% anticipates the organic decomposition, reducing the combustion event in the final calcination. Furthermore, FTIR-PAS, XRD and SEM results showed that organic matter amount was reduced in the Fe (III)-doped TiO2 sample, which reduced the rutile phase amount and increased the reactivity and crystallinity of the powder samples.

Untersuchungen zur Löslichkeit von Kobalt und Eisen in TiO 2-Bulk sowie in TiO 2-Nanoproben und deren Einfluss auf die magnetischen Eigenschaften

Co- und Fe-dotierte Rutil- und Anatas-Bulkproben wurden über einen Sol-Gel Prozess und anschließende thermische Behandlung dargestellt und auf ihre Zugehörigkeit zu der Gruppe der verdünnten magnetischen Oxide untersucht. Die Untersuchungen der dotierten Rutil-Proben mittels Röntgenbeugung, Elektronenmikroskopie und magnetischen Methoden zeigen, dass die Löslichkeit von Co und Fe in der TiO2-Modifikation Rutil sehr gering ist. Oberhalb von 1at% Co bzw. Fe wird neben Rutil die Bildung der Oxide CoTiO3 bzw. Fe2TiO5 beobachtet. Weitere thermische Behandlung im Argon-H2-Strom führte aufgrund der Bildung von metallischem Co bzw. Fe zu einem ferromagnetischen Verhalten. Die TiO2-Modifikation Anatas besitzt eine höhere Löslichkeit, so dass erst oberhalb von 4at% Co bzw. 10at% Fe die Phasen Co3O4 bzw. FeTiO3 neben Anatas auftreten. Entsprechende Proben zeigen ein paramagnetisches Verhalten. Oberhalb der Löslichkeitsgrenze führt die Reduktion im Argon-H2-Strom zu einem ferromagnetischen Verhalten, welches auf metallisches Co bzw. Fe zurückzuführen ist. Analog zu den Bulkproben wurden Co- und Fe-dotierte TiO2-Nanodrähte hergestellt. Das magnetische Verhalten der Fe-dotierten TiO2-Nanodrähte entspricht dem der Fe-dotierten Anatas-Bulkproben. Dagegen führt die Co-Dotierung nicht zu einem Einbau in die TiO2-Nanodrähte, sondern zur Bildung von CoOx-Nanopartikeln. Die entsprechenden Proben zeigen ein schwach ferromagnetisches Verhalten. Dies ist jedoch nicht auf eine ferromagnetische Dotierung der TiO2-Nanodrähte zurückzuführen, sondern auf nicht kompensierte Momente an den Oberflächen der als Verunreinigungen auftretenden CoOx-Nanopartikel. Zusammenfassend wird festgestellt, dass die Löslichkeit von Co und Fe in TiO2 für die Ausbildung eines ferromagnetischen Verhaltens zu gering ist. Der beobachtete Ferromagnetismus lässt sich eindeutig auf magnetische Verunreinigungen zurückführen. Somit können die dotierten TiO2 Proben nicht den verdünnten magnetischen Oxiden zugeordnet werden.

New reactants and improved catalysts for maleic anhydride synthesis

The role of the amount of Nb, used as a dopant for VPP, and how its presence may affect the generation of the active and selective δ-VOPO4 at the VPP surface under reaction conditions, was investigated, employing ex-situ and in-situ characterisation techniques. We found that Nb indeed may favour, under specific conditions, the generation of the desired δ-VOPO4 compound; however, its effect of enhancement of catalytic behaviour was not simply proportional to its concentration. In order to better understand how Nb may affect the generation of the active phase, we prepared V/Nb mixed phosphates; the formation of a solid solution was possible only under specific conditions, with a limited reciprocal dissolution of the two elements. We concluded that even though the incorporation of small amounts of Nb5+ in the VOPO4 (and also of V5+ in NbOPO4) cannot be excluded, a phenomenon which might favour the generation of the desired δ-VOPO4 compound, however the main role of Nb5+ was related to a modification of the redox properties of V4+ in the VPP, and specifically of the redox potential associated to the couple V4+/V5+. This led to a catalyst that during reaction was more oxidized than the corresponding undoped VPP, which under specific reaction conditions allowed obtain a better selectivity to MA. Oppositely, an excessive oxidation of VPP (catalysts having high [Nb]) affected negatively the MA selectivity, because of the excessive formation of COx. A preliminary study regarding the oxidehydration of 1-butanol into MA was carried out testing various catalysts: the best catalyst resulted VPP; however the MA selectivity was lower than that obtained from n-butane. With in-situ/operando Raman study of the Nb-doped and undoped catalysts we verified that the redox cycle involves the VPP and the δ-VOPO4 compounds, that the reoxidation step of V4+ in VPP is the rate-determining one.

Effects of Ultrasound Irradiation on the Synthesis of Metal Oxide Nanostructures

High intensity ultrasound can be used for the production of novel nanomaterials, including metal oxides. According to previous works in this field, the most notable effects are consequence of acoustic cavitation. In this context, we have studied the preparation of different materials in the presence of ultrasound, including N-doped TiO2 nanopowder, NiTiO3 nanorods and MnOx thin films. Ultrasound did not show a significant effect in all the cases. Exclusively for NiTiO3 nanorods a reduction of the final particle size occurs upon ultrasonic irradiation. From these results, it can be concluded that the ultrasound irradiation does not always play a key role during the synthesis of metal oxides. The effects seem to be particularly relevant in those cases where mass transport is highly hindered and in those procedures that require the rupture of nanoparticle aggregates to obtain a homogenous dispersion.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt–titanate nanotubes

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na+ -> Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti4+ ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na+ ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Highly textured Sr, Nb, co-doped BiFeO3 thin films grown on SrRuO3/Si substrates by rf-sputtering

In this study, (011)-highly oriented Sr, Nb co-doped BiFeO3 (BFO) thin films were successfully grown on SrRuO3/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of 5.3 nm and average grain sizes of 65-70 nm for samples with different thicknesses. Remanent polarization values (2Pr) of 54 lC cm 2 at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe3þ/Fe2þ trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/ SrRuO3/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

Spectroscopic features of erbium-doped CaM2O6 (M = Nb, Ta) single crystal fibers grown by the laser-heated pedestal growth technique

Erbium-doped single crystal fibers, with low phonon energy and fairly high absorption and emission cross sections are interesting laser active media, for compact, near-infrared and/or upconversion lasers. In this work, high optical quality Er3+-doped CaNb2O6 and CaTa2O6 single crystal fibers were successfully grown by the versatile laser-heated pedestal growth technique, and characterized from the structural and spectroscopic points of view. The results indicate that these crystal fiber compositions, which had not been explored so far, offer potential applications, not only as laser active media, but also in other optical devices. (c) 2007 Elsevier B.V. All rights reserved.

Aspects of solid state formation and properties of Sn(0.9)Ti(0.1)O(2) system doped with CoO and Nb(2)O(5)

The effect of calcination temperature during the formation of the solid solution Sn(0.9)Ti(0.1)O(2) doped with 1.00 mol % CoO and 0.05 mol % Nb(2)O(5) is presented. The structural characteristics of this system were studied using X-ray diffraction, and the changes in phase formation were analyzed using the Rietveld method. With an increase in calcination temperature, there is increasing miscibility of Ti into the (Ti,Sn)O(2) phase and near 1000 degrees C, and the remaining TiO(2) (anatase) was transformed into the rutile phase. The sintering process, monitored using dilatometry, suggests two mass transport mechanisms, one activated close to 900 degrees C associated with the presence of TiO(2) (anatase) and the second mechanism, occurring between 1200 and 1300 degrees C, is attributed to a faster grain boundary diffusion caused by oxygen vacancies. (C) 2008 International Centre for Diffraction Data.

An ab initio study of oxygen vacancies and doping process of Nb and Cr atoms on TiO2 (110) surface models

We theoretically investigated how the formation of oxygen vacancies and the addition of niobium and chromium atoms as dopants modify the varistor properties of TiO2. The calculations were carried out at the HF level using a contracted basis set, developed by Huzinaga et al.. to represent the atomic centers on the (110) surface for the large (TiO2)(15) cluster model. The change of the values for the net atomic charges and band gap after oxygen vacancy formation and the presence of dopants in the lattice are analyzed and discussed. It is shown that the formation of oxygen vacancies decreases the band gap while an opposite effect is found when dopants are located in the reduced surface. The theoretical results are compared with available experimental data. A plausible explanation of the varistor behavior of this system is proposed. (C) 1997 John Wiley & Sons, Inc.

Electrical and micro structural properties of (Zn, Nb, Fe)-doped SnO2 varistor systems

The electrical and microstructural properties of SnO2-based varistors with the addition of 0.025 and 0.050 mol% of Fe2O3 have been characterised. Electric field (E) versus current density (J) curves showed that the effect of Fe2O3 addition is to increase both the non-linear coefficient and the breakdown voltage. Variations in the potential barrier height were inferred from impedance spectroscopy (IS) analysis. Through transmission electron microscopy (TEM), the presence of precipitates of secondary phases was confirmed. Samples with precipitates displayed poor electrical properties. (c) 2004 Elsevier Ltd and Techna Group S.r.l. All rights reserved.