Reactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110)

Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO2 clusters, Ti2O4, Ti3O6 and Ti4O8 supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO2, demonstrating the usefulness of this composite system for redox catalysis.

An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

Nanocrystalline SnO2-based, UVB-activated, colourimetric oxygen indicator

Nanocrystalline SnO2, ncSnO(2), is used as a photosensitiser in a colourimetric O-2 indicator that comprises a sacrificial electron donor, glycerol, a redox dye, methylene blue (MB), and an encapsulating polymer, hydroxyethyl cellulose (HEC). Upon exposure to a burst of UVB light the indicator is activated (photo-bleached) as the MB is photoreduced by the ncSnO(2) particles. In the absence of oxygen, the film stays bleached, but recovers its original colour upon exposure to oxygen. Unlike its TiO2-based predecessor, the HEC/glycerol/MB/ncSnO(2) O-2 indicator is not activated by UVA light from white fluorescent lamps, but is by UVB light. This feature provides much greater control in the activation of the indicator. Other work shows the rate of activation depends upon I-0.75, where I is the UVB irradiance, indicating a partial dependence upon the electron-hole recombination process. The half-life of the recovery of the original colour of a UV-activated film, t(50), is directly proportional to the ambient level of oxygen. The advantages of using this indicator in modified atmosphere packaging as a possible quality assurance indicator are discussed briefly. (c) 2008 Elsevier B.V. All rights reserved.

Density functional theory study of mixed-phase TiO2: heterostructures and electronic properties

In this work, density functional theory calculations have been performed to study the geometric, electronic, and energetic properties of two-phase TiO2 composites built by joining two single-phase TiO2 slabs, aiming at verifying possible improvement of the photo-activities of the composites through phase separation of excitons. We find that such desired electronic properties can be determined by several factors. When both the HOMO and LUMO levels of one of the two single-phase TiO2 slabs are higher than the corresponding ones of the other, the composite may have native electronic structures with phase-separated HOMO-LUMO states, especially when the two slabs exhibit highly matched surface lattices. For those pairs of TiO2 slabs with the HOMO and LUMO levels of one phase being within the range of those of the other, though the energetically favored composite give HOMO-LUMO states within one phase, one may still be able to separate them and move the HOMO state to the interface region by destabilizing the interactions between the two slabs.

Atmospheric Pressure DC Plasma Processing of TIO2/PEDOT:PSS Nanocomposites

In this work we demonstrate the synthesis of a TiO2/PEDOT:PSS nanocomposite material in aqueous solution through atmospheric pressure direct current (DC) plasma processing at room temperature. The dispersion of the TiO2 nanoparticles is enhanced after microplasma processing, and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. We have observed increased TiO2/PEDOT:PSS nanocomposite electrical conductivity due to microplasma processing. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are thought to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer bonding, which is expected to have a significant benefit in materials processing with inorganic nanoparticles for wide range of applications.

Investigations on TiO2 Based Nanocomposites as Potential Photonic Materials

This Study overviews the basics of TiO2with respect to its structure, properties and applications. A brief account of its structural, electronic and optical properties is provided. Various emerging technological applications utilising TiO2 is also discussed.Till now, exceptionally large number of fundamental studies and application-oriented research and developments has been carried out by many researchers worldwide in TiO2 with its low-dimensional nanomaterial form due to its various novel properties. These nanostructured materials have shown many favourable properties for potential applications, including pollutant photocatalytic decomposition, photovoltaic cells, sensors and so on. This thesis aims to make an in-depth investigation on different linear and nonlinear optical and structural characteristics of different phases of TiO2. Correspondingly, extensive challenges to synthesise different high quality TiO2 nanostructure derivatives such as nanotubes, nanospheres, nanoflowers etc. are continuing. Here, different nanostructures of anatase TiO2 were synthesised and analysed. Morphologically different nanostructures were found to have different impact on their physical and electronic properties such as varied surface area, dissimilar quantum confinement and hence diverged suitability for different applications. In view of the advantages of TiO2, it can act as an excellent matrix for nanoparticle composite films. These composite films may lead to several advantageous functional optical characteristics. Detailed investigations of these kinds of nanocomposites were also performed, only to find that these nanocomposites showed higher adeptness than their parent material. Fine tuning of these parameters helps researchers to achieve high proficiency in their respective applications. These innumerable opportunities aims to encompass the new progress in studies related to TiO2 for an efficient utilization in photo-catalytic or photo-voltaic applications under visible light, accentuate the future trends of TiO2-research in the environment as well as energy related fields serving promising applications benefitting the mankind. The last section of the thesis discusses the applicability of analysed nanomaterials for dye sensitised solar cells followed by future suggestions.

Mechanochemical synthesis of nanocrystalline SnO2-ZnO photocatalysts

Mechanochemical processing of anhydrous chloride precursors with Na₂CO₃ has been investigated as a means of manufacturing nanocrystalline SnO₂ doped ZnO photocatalysts. High-energy milling and heat-treatment of a 0.1SnCl₂+0.9ZnCl₂+Na₂CO₃+4NaCl reactant mixture was found to result in the formation of a composite powder consisting of oxide grains embedded within a matrix of NaCl. Subsequent washing with deionized water resulted in removal of the NaCl matrix phase and partial hydration of the oxide reaction product with the consequent formation of ZnSn(OH)₆. The extent of this hydration reaction was found to decrease in a linear fashion with the temperature of the post-milling heat-treatment over the range of 400–700 °C. For a heat-treatment temperature of 700 °C, the SnO₂ doped ZnO powder was found to exhibit significantly higher photocatalytic activity than either single-phase SnO₂ or ZnO powders that were synthesized using similar processing conditions. The heightened photocatalytic activity of the SnO₂ doped ZnO was attributed to its higher specific surface area and the enhanced charge separation arising from the coupling of ZnO with SnO₂.

Ion transport in polymer electrolytes containing nanoparticulate TiO2 : The influence of polymer morphology

Recent studies have shown that composite polymer electrolytes, formed by dispersing nanosized ceramic particles in polyether-based electrolytes, have improved ion transport properties as compared to their unfilled analogues. In the present study polymer electrolytes with different loadings of nano-sized ceramic particles (TiO₂) and different polymer chemistry and morphology have been investigated. Of special interest are filler induced effects on polymer, solvent and cationic mobility. Partly crystalline polymer electrolytes based on poly(ethylene oxide) have been compared to fully amorphous polymer electrolytes based on a polyether urethane, as well as gel electrolytes based on PMMA. ⁷Li pfg-NMR, linewidth and spin–spin relaxation times as well as ¹H pfg-NMR and spin–spin relaxation times, were measured as a function of temperature and composition. The ¹H spin–spin relaxation measurements reveal increased average polymer mobility with the addition of filler up to a maximum at 4 and 8 wt.% TiO₂ for the fully amorphous and the partly crystalline electrolytes, respectively. The ⁷Li linewidth measurements for the fully amorphous system show a broadening of the linewidth with addition of filler. Based on variable temperature measurements this broadening is interpreted as a result of the inhomogeneity introduced by the filler particles. Pulsed field gradient (pfg) diffusion measurements were employed to determine ion and solvent self-diffusion coefficients. In the case of the PMMA-based gel electrolyte and the fully amorphous electrolytes enhanced cation self-diffusion was observed upon addition of TiO₂.

Enhancement of ion dynamics in PMMA-based gels with addition of TiO2 nano-particles

Solvent and ion dynamics in PMMA based gels have been investigated as a function of the loading of nanosized TiO₂ particles. The gels have a molar ratio of 46.5:19:4.5:30 of ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate and PMMA, respectively. A series of samples with 0, 4, 6 and 8 wt.% TiO₂ filler were investigated. The diffusion coefficients for the lithium ions and for the two solvents (EC and PC) were investigated by pfg-NMR. It was shown that the addition of filler to the gel electrolytes enhances the diffusion of the cations, while the diffusion of the solvents remains constant. Raman measurements show no significant changes in ion–ion interactions with the addition of fillers, while the ionic conductivity is seen to decrease. However, the sample with 8 wt.% TiO₂ had a conductivity close to that of the unfilled sample.

Synergic effect within n-type inorganic–p-type organic nano-hybrids in gas sensors

This paper describes the exploration of a synergic effect within n-type inorganic–p-type organic nanohybrids in gas sensors. One-dimensional (1D) n-type SnO2–p-type PPy composite nanofibers were prepared by combining the electrospinning and polymerization techniques, and taken as models to explore the synergic effect during the sensing measurement. Outstanding sensing performances, such as large responses and low detection limits (20 ppb for ammonia) were obtained. A plausible mechanism for the synergic effect was established by introducing p–n junction theory to the systems. Moreover, interfacial metal (Ag) nanoparticles were introduced into the n-type SnO2–p-type PPy nano-hybrids to further supplement and verify our theory. The generality of this mechanism was further verified using TiO2–PPy and TiO2–Au–PPy nano-hybrids. We believe that our results can construct a powerful platform to better understand the relationship between the microstructures and their gas sensing performances.

Photostability of wool fabrics coated with pure and modified TiO2 colloids

The surface of wool fabrics was coated with TiO2 and TiO2-based nanocomposite colloids and the impact of this coating on the photostability of wool was investigated. TiO2 along with TiO2/Metal and TiO2/Metal/SiO2 sols were synthesized through a low-temperature sol-gel method and applied to fabrics. Composite colloids were synthesized through integrating the silica and three noble metals of silver (Ag), gold (Au) and platinum (Pt) into the synthesis process of sols. Four different molar ratios of Metal to TiO2 (0.01%, 0.1%, 0.5% and 1%) were used to elucidate the role of metal type and amount on the obtained features. Photostability and UV protection features of fabrics were evaluated through measuring the photo-induced chemiluminescence (PICL), photoyellowing rate and ultraviolet protection factor (UPF) of fabrics. PICL and photoyellowing tests were carried out under UVA and UVC light sources, respectively. PICL profiles demonstrated that the presence of pure and modified TiO2 nanoparticles on fabrics reduced the intensity of PICL peak indicating a lower amount of polymer free radicals in coated wool, compared to that of pristine fabric. Moreover, a higher PICL peak intensity as well as photoyellowing rate was observed on fabrics coated with modified colloids in comparison with pure TiO2. The surface morphology of fabrics was further characterized using FESEM images.

Reprint of: photostability of wool fabrics coated with pure and modified TiO2 colloids

The surface of wool fabrics was coated with TiO2 and TiO2-based nanocomposite colloids and the impact of this coating on the photostability of wool was investigated. TiO2 along with TiO2/Metal and TiO2/Metal/SiO2 sols were synthesized through a low-temperature sol-gel method and applied to fabrics. Composite colloids were synthesized through integrating the silica and three noble metals of silver (Ag), gold (Au) and platinum (Pt) into the synthesis process of sols. Four different molar ratios of Metal to TiO2 (0.01%, 0.1%, 0.5% and 1%) were used to elucidate the role of metal type and amount on the obtained features. Photostability and UV protection features of fabrics were evaluated through measuring the photo-induced chemiluminescence (PICL), photoyellowing rate and ultraviolet protection factor (UPF) of fabrics. PICL and photoyellowing tests were carried out under UVA and UVC light sources, respectively. PICL profiles demonstrated that the presence of pure and modified TiO2 nanoparticles on fabrics reduced the intensity of PICL peak indicating a lower amount of polymer free radicals in coated wool, compared to that of pristine fabric. Moreover, a higher PICL peak intensity as well as photoyellowing rate was observed on fabrics coated with modified colloids in comparison with pure TiO2. The surface morphology of fabrics was further characterized using FESEM images.

Obtenção e Caracterização Físico-Química do Sistema Compósito PEG-TiO2

Hybrid systems formed from polymers and transition metals have now their physical and chemical properties extensively investigated for use in electronic devices. In this work, Titanium Dioxide (TiO2) from the precursor of titanium tetrabutoxide and the composite system Poly(Ethylene Glycol)-Titanium Dioxide (TiO2-PEG) were synthesized by sol-gel method. The PEG as acquired and TiO2 and composites powders were analyzed by X-Ray Diffraction (XRD), Spectroscopy in the Infrared region with Fourier transform (IRFT), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). In the XRD analysis were observed in the TiO2 crystal faces of one of its polymorphs - anatase phase, crystal planes in Poly (Ethylene Glycol) with considerable intensity and in the composite systems the mixture of crystal faces of their precursors isolated and reduction of crystallinity. The TG / DTG suggested increasing the thermal instability of PEG in the composite powders as TiO2 is incorporated into the system. Spectral analysis presented in the infrared overlapping bands for the polymer and metal oxide, reducing the intensity of symmetric stretching of ligand groups in the main chain polymer and angular deformations; were observed using SEM micrographs of the morphological changes suffered by composite systems with the variation of the oxide concentration. Analyses by impedance spectroscopy indicated that the increased conductivity in composite occurs in line with the addition of the metal oxide concentration in the composite system

SnO2 nanoparticles functionalized in amorphous silica and glass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Fabrication of coaxial TiO2/Sb2S3 nanowire hybrids for efficient nanostructured organic- inorganic thin film photovoltaics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)