Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (I 10), (0 10), (10 1) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For, comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximate to (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

TiO2/CuO films obtained by citrate precursor method for photocatalytic application

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

Nanostructured TiO2-based composites for light absorption

Metal oxidenanocomposites were prepared by two different routes: polyol and sol-gel. Characterization by X ray diffraction showed that the first processproducesdirectly a two-phase material, while the sol-gelpowder never showed second phase below 600 degrees C. Light spectroscopy of the treated powders indicated similarities for the processed materials. Although the overall material compositions are about the same, different structural characteristics are found for each processing. With the exception of Ti-Zn materials, all the double metal oxide powders showed higher absorbance than either TiO2 powder.

Synthesis and characterization of nanostructured TiO2-SnO2 composite

Nanostructured composites based on titanium dioxide have been studied in order to improve optical and photo-catalytic properties, as well as their performance in gas sensors. In this work, titanium and tin dioxides were simultaneously synthesized by the polyol method resulting in TiO2 platelet coated with SnO2 nanoparticles as was observed by scanning electron microscopy. The thermal analysis showed that the combined synthesis promotes more easily the crystallization of the TiO2 rutile phase. The composite obtained after heat treatment at 500 degrees C showed to be formed of almost only rutile phases of both oxides. The optical properties analyzed by UV-Vis spectroscopy showed that the combined oxides have higher absorbance, which reinforces a model found in the literature based on the flow of photo-generated electrons to the conduction band of SnO2 delaying the recombination of charges.

Enhanced photoabsorption properties of composites of Ti/TiO2 nanotubes decorated by Sb2S3 and improvement of degradation of hair dye

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

Synthesis and characterization of nanostructured TiO2-SnO2 composite

Nanostructured composites based on titanium dioxide have been studied in order to improve optical and photo-catalytic properties, as well as their performance in gas sensors. In this work, titanium and tin dioxides were simultaneously synthesized by the polyol method resulting in TiO2 platelet coated with SnO2 nanoparticles as was observed by scanning electron microscopy. The thermal analysis showed that the combined synthesis promotes more easily the crystallization of the TiO2 rutile phase. The composite obtained after heat treatment at 500 °C showed to be formed of almost only rutile phases of both oxides. The optical properties analyzed by UV-Vis spectroscopy showed that the combined oxides have higher absorbance, which reinforces a model found in the literature based on the flow of photo-generated electrons to the conduction band of SnO2 delaying the recombination of charges.

Photoluminescent CaCu3Ti4O12-Based Thin Films Synthesized by a Sol-Gel Method

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.

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.

Sintering mechanisms of ZrO2 center dot MgO with addition of TiO2 and CuO

Substitutions of Ti and Cu in ZrO2.MgO (Z), cause transformation from monoclinic (m) to cubic (c) and tetragonal (t). According to the vacancy model and solid Solution formation models, neither CuO nor TiO2 cause zirconia stabilization, which derives front other phenomena. Data analysis by TMA using the CRH (constant rate of heating) method shows a solid state reaction of ZrO2.MgO.TiO2 (Z.TiO2) demonstrating a dominant mechanism of volume diffusion (n = 1). However, the sintering of ZrO2.MgO.CuO (Z.CuO) shows a viscous flow mechanism (n = 0), a similar phenomena to that of by sintering of glass. Transformations, such as: CuO to Cu2O at 1000 degreesC, ZrO2 (m) to ZrO2 (t) at 1100 degreesC and Cu2O (s) to Cu2O (l) at 1230 degreesC cause successive rearrangements of microstructure inside of region I (sintering process) and lead to interpretation errors when the Bannister equation is used. (C) 2003 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Properties of one modified composite resin by TiO2 nanoparticles

The purpose of this study was to evaluate the compressive strength and color changes of one composite resin modified by TiO2 nanoparticles and their distribution by SEM.

Electrical relaxation in proton conductor composites based on (NH4)H2PO4/TiO2

We report on electrical relaxation measurements of (1-x)NH4H2PO4-xTiO(2) (x = 0.1) composites by admittance spectroscopy, in the 40-Hz-5-MHz frequency range and at temperatures between 303 and 563 K. Simultaneous thermal and electrical measurements on the composites identify a stable crystalline phase between 373 and 463 K. The real part of the conductivity, sigma', shows a power-law frequency dependence below 523 K, which is well described by Jonscher's expression sigma' = sigma(0)(1 + (omega/omega(p))(n)), where sigma(0) is the dc conductivity, omega(p)/2 pi = f(p) is a characteristic relaxation frequency, and n is a fractional exponent between 0 and 1. Both sigma(0) and f(p) are thermally activated with nearly the same activation energy in the II region, indicating that the dispersive conductivity originates from the migration of protons. However, activation energies decrease from 0.55 to 0.35 eV and n increases toward 1.0, as the concentration of TiO2 nanoparticles increases, thus, enhancing cooperative correlation among moving ions. The highest dc conductivity is obtained for the composite x = 0.05 concentration, with values above room temperature about three orders of magnitude higher than that of crystalline NH4H2PO4 (ADP), reaching values on the order of 0.1 (Omega cm)(-1) above 543 K.

TiO2-Cu photocatalysts: A study on the long- and short-range chemical environment of the dopant

In this study, the short- and long-range chemical environments of Cu dopant in TiO2 photocatalyst have been investigated. The Cu-doped and undoped TiO2 specimens were prepared by the sol-gel approach employing CuSO4·5H2O and Ti(O-iPr)4 precursors and subjecting the dried gels to thermal treatment at 400 and 500 C. The photocatalytic activity, investigated by methylene blue degradation under sunlight irradiation, showed a significantly higher efficiency of Cu-doped samples than that of pure TiO2. The X-ray diffraction results showed the presence of anatase phase for samples prepared at 400 and 500 C. No crystalline CuSO4 phase was detected below 500 C. It was also found that doping decreases the crystallite size in the (004) and (101) directions. Infrared spectroscopy results indicated that the chemical environment of sulfate changes as a function of thermal treatment, and UV-vis spectra showed that the band gap decreases with thermal treatment and Cu doping, showing the lowest value for the 400 C sample. X-ray absorption fine structure measurements and analysis refinements revealed that even after thermal treatment and photocatalytic assays, the Cu2+ local order is similar to that of CuSO4, containing, however, oxygen vacancies. X-ray photoelectron spectroscopy data, limited to the near surface region of the catalyst, evidenced, besides CuSO4, the presence of Cu1+ and CuO phases, indicating the active role of Cu in the TiO2 lattice. © 2013 Springer Science+Business Media New York.

Síntese e caracterização de ZnO/TiO2 nanoestruturado

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)