Ecotoxicology of Nano-TiO2 An Evaluation of its Toxicity to Organisms of Aquatic Ecosystems

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Layer by layer TiO2 thin films and photodegradation of Congo red

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural and Electronic Effects of Incorporating Mn in TiO2 Films Grown by Sputtering: Anatase versus Rutile

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

ZnO-TiO2 composite formed by mixed oxides via polyol

Among the researches on preparation and test of nanostructured materials, titanium dioxide and zinc oxide have been the most frequent studied oxides. In order to extend their properties, composites have been prepared using three different methods: Polyol Method, Sol-gel Process and a combination of the two processes (hybrid process). Recent research showed best properties in composite materials than in pure oxides. In this work is presented the preparation and the structural characterization of ZnO-TiO2 composite nanostructures to be tested for their performance in electrocatalysis and in further trial on photovoltaic cells.

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

Static simulation of bulk and selected surfaces of anatase TiO2

A theoretical investigation has been carried out to characterize bulk and selected surfaces of anatase TiO2. The calculations are performed using a B3LYP hybrid functional and 6-31G basis set within the periodic density functional approximation. Optimization procedures have been employed to determine the equilibrium geometry of the crystal and slab surface models. The compressibility, band structure, and the bulk and surface charge distributions are reported. The surface relative energies are identified to follow the sequence: (001) < (101) < (100) much less than (110) < < < (111), from the most stable surface to the least stable one. Relaxation of (001) and (101) surfaces are moderate, with no displacements exceeding; approximate to0.19 Angstrom. The theoretical results are compared with previous theoretical studies and available experimental data. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Preparation of Al2TiO5-Al2O3 and Al2TiO5-Al2O3-TiO2 Ceramics by High-Energy Ball Milling and Sintering

The present work reports on the preparation of Al2O3-TiO2 ceramics by high-energy ball milling and sintering, varying the molar fraction in 1:1 and 3:1. The powder mixtures were processed in a planetary Fritsch P-5 ball mill using silicon nitride balls (10 mm diameter) and vials (225 mL), rotary speed of 250 rpm and a ball-to-powder weight ratio of 5:1. Samples were collected into the vial after different milling times. The milled powders were uniaxially compacted and sintered at 1300 and 1500 degrees C for 4h. The milled and sintered materials were characterized by X-ray diffraction and electron scanning microscopy (SEM). Results indicated that the intensity of Al2O3 and TiO2 peaks were reduced for longer milling times, suggesting that nanosized particles can be achieved. The densification of Al2O3-TiO2 ceramics was higher than 98% over the relative density in samples sintered at 1500 degrees C for 4h, which presented the formation of Al2TiO5.

Enhanced ferroelectric properties of La-substituted BiFeO3 thin films on LaSrCoO3/Pt/TiO2/SiO2/Si (100) substrates prepared by the soft chemical method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Degradation of [D-Leu]-Microcystin-LR by solar heterogeneous photocatalysis (TiO2)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Activity and characterization by XPS, HR-TEM, Raman spectroscopy, and BET surface area of CuO/CeO2-TiO2 catalysts

Structural and textural studies of a CuO/TiO2 System modified by cerium oxide were conducted using Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N-2 absorption (BET specific surface area). The introduction of a minor amount of CeO2 (Ce0.09Ti0.82O1.91CU0.09 sample) resulted in a material with the maximum surface area value. The results of Raman spectroscopy revealed the presence of only two crystalline phases, TiO2 anatase and CeO2 cerianite, with well-dispersed copper species. TEM micrographs showed a trend toward smaller TiO2 crystallites when the cerium oxide content was increased. The XPS analysis indicated the rise of a second peak in Ti 2p spectra with the increasing amount of CeO2 located at higher binding energies than that due to the Till in a tetragonal symmetry. The CuO/TiO2 system modified by CeO2 displayed a superior performance for methanol dehydrogenation than the copper catalyst supported only on TiO2 or CeO2.

X-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction characterization of CuO-TiO2-CeO2 catalyst system

X-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and x-ray absorption spectroscopy (XAS) techniques have been applied to characterize the surface composition and structure of a series of CuO-TiO2-CeO2 catalysts. For a small loading of cerium, ceria was mainly dispersed on the titania surface and a minor amount of CeO2 crystallite appeared. At higher loading of cerium, the CeO2 phase increased and the atomic Ce/Ti ratio values were smaller than the nominal composition, as a consequence of cerium agglomeration. This result suggests that only a fraction of cerium can be spread on the titania surface. For titanium-based mixed oxide, we observed that cerium is found as Ce3+ uniquely on the surface. The atomic Cu/(Ce+Ti) ratio values showed no influence from cerium concentration on the dispersion of copper, although the copper on the surface was shown to be dependent on the cerium species. For samples with a high amount of cerium, XPS analysis indicated the raise of second titanium species due cerium with spin-orbit components at higher binding energies than those presented by Ti4+ in a tetragonal structure. The structural results obtained by XAS are consistent with those obtained by XRD and XPS. (C) 2001 American Vacuum Society.

Photoelectrocatalytic treatment of p-nitrophenol using Ti/TiO2 thin-film electrode

The photoelectrochemical degradation of p-nitrophenol (PNP) was investigated using titanium dioxide thin-film photoelectrode. The effects of different supporting electrolytes, pH, applied potential and PNP concentration were examined and discussed. Complete photodegradation was obtained in perchlorate medium at pH 2 when the photoanode was biased at +1.0 V (versus SCE) during a 3-h experiment. Under these conditions, carbon removal of approximately 60% was achieved. (C) 2005 Elsevier B.V. All rights reserved.

V2O5/TiO2 catalyst xerogels: Method of preparation and characterization

This work describes a modified sol-gel method for the preparation of V2O5/TiO2 catalysts. The samples have been characterized by N-2 adsorption at 77 K, X-ray Diffractometry (XRD), Scanning Electronic Microscopy (SEM/EDX) and Fourier Transform Infrared Spectroscopy (FT-IR). The surface area increases with the vanadia loading from 24 m(2) g(-1) for pure TiO2 to 87 m(2) g(-1) for 9 wt% of V2O5. The rutile form is predominant for pure TiO2 but becomes enriched with anatase phase when vanadia loading is increased. No crystalline V2O5 phase was observed in the diffractograms of the catalysts. Analysis by SEM showed heterogeneous granulation of particles with high vanadium dispersion. Two species of surface vanadium were observed by FT-IR spectroscopy: a monomeric vanadyl and polymeric vanadates. The vanadyl/vanadate ratio remains practically constant. Ethanol oxidation was used as a catalytic test in a temperature range from 350 to 560 K. The catalytic activity starts around 380 K. For the sample with 9 wt% of vanadia, the conversion of ethanol into acetaldehyde as the main product was approximately 90% at 473 K.

Studies on the adsorption and kinetics of photodegradation of a model compound for heterogeneous photocatalysis onto TiO2

An investigation was made on the adsorption and kinetics of photodegradation of potassium hydrogenphthalate in an aqueous suspension of TiO2. Two models, Langmuir and Freundlich, were used to describe the adsorption process and the model proposed by Langmuir-Hinshelwood (L-H) was employed to describe the kinetics of the photodecomposition reactions of hydrogenphthalate. The results of the adsorptions were fitted to the models proposed by Langmuir and Freundlich. Adsorption was found to be a function of the temperature, with adsorption capacity increasing from 2.4 to 4.5 mg/g when the temperature rose from 20 to 30 degrees C. The kinetic model indicates that the rate constant, k, of the first order reaction, is high in the 10.0 to 100 mg/l interval, which is coherent with the low value of the adsorption constant, K. The results fitted to the L-H model led to an equation that, within the range of concentrations studied here, theoretically allows one to evaluate the photodegradation rate. (c) 2005 Elsevier Ltd. All rights reserved.

Chemical and structural characterization of V2O5/TiO2 catalysts

A series of V2O5/TiO2 samples was synthesized by sol-gel and impregnation methods with different contents of vanadia. These samples were characterized by x-ray diffraction (XRD), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), and electronic paramagnetic resonance (EPR). XRD detected rutile as the predominant phase for pure TiO2 prepared by the sol-gel method. The structure changed to anatase when the vanadia loading was increased. Also, anatase was the predominant phase for samples obtained by the impregnation method. Raman measurements identified two species of surface vanadium: monomeric vanadyl (V4+) and polymeric vanadates (V5+). XPS results indicated that Ti ions were in octahedral position surrounded by oxygen ions. The V/Ti atomic ratios showed that V ions were highly dispersed on the vanadia/titania surface obtained by the sol-gel method. EPR analysis detected three V4+ ion types: two of them were located in axially symmetric sites substituting for Ti4+ ions in the rutile structure, and the third one was characterized by magnetically interacting V4+ ions in the form of pairs or clusters. A partial oxidation of V4+ to V5+ was evident from EPR analysis for materials with higher concentrations of vanadium. (C) 2001 American Vacuum Society.