Preparation and characterisation of novel thick sol-gel titania film photocatalysts

The preparation and characterization of thick (9 mum), clear, mechanically robust and photocatalytically active films of nanocrystalline anatase titania are described. XRD and SEM analysis show the films comprise 13 nm particles of anatase TiO2. Thin (54 nm) films of the 'paste' TiO2, along with sol-gel titania films made by a more traditional route are also prepared and characterised. All titania films mediate the photocatalytic destruction of stearic acid with a quantum yield of 0.0016 +/- 0.0003. using either 365 nm (i.e. BLB) or 254 nm (germicidal) light. P25 TiO2 films also appear to mediate the same process with a similar formal quantum efficiency. Of all the films tested, the thick paste TiO2 films are the most ideally suited for use with near UV light, for reasons which are discussed. All the titania films tested exhibit photoinduced superhydrophilicity.

Atmospheric pressure chemical vapour deposition of titanium dioxide coatings on glass

Atmospheric pressure chemical vapour deposition of titanium dioxide coatings on glass substrates was achieved by the reaction of TiCl4 and a co-oxygen source (MeOH, EtOH, (PrOH)-Pr-i or H2O) at 500-650degreesC. The coatings show excellent uniformity, surface coverage and adherence. Growth rates were of the order of 0.3 mum min(-1) at 500degreesC. All films are crystalline and single phase with XRD showing the anatase TiO2 diffraction pattern; a = 3.78(1), c = 9.51(1) Angstrom. Optically, the films show minimal reflectivity from 300-1600 nm and 50-80% total transmission from 300-800 nm. Contact angles are in the range 20-40degrees for as-prepared films and 1-10degrees after 30 min irradiation at 254 nm. All of the films show significant photocatalyic activity as regards the destruction of an overlayer of stearic acid.

Universal tight binding model for chemical reactions in solution and at surfaces. III. Stoichiometric and reduced surfaces of titania and the adsorption of water

We demonstrate a model for stoichiometric and reduced titanium dioxide intended for use in molecular dynamics and other atomistic simulations and based in the polarizable ion tight binding theory. This extends the model introduced in two previous papers from molecular and liquid applications into the solid state, thus completing the task of providing a comprehensive and unified scheme for studying chemical reactions, particularly aimed at problems in catalysis and electrochemistry. As before, experimental results are given priority over theoretical ones in selecting targets for model fitting, for which we used crystal parameters and band gaps of titania bulk polymorphs, rutile and anatase. The model is applied to six low index titania surfaces, with and without oxygen vacancies and adsorbed water molecules, both in dissociated and non-dissociated states. Finally, we present the results of molecular dynamics simulation of an anatase cluster with a number of adsorbed water molecules and discuss the role of edge and corner atoms of the cluster. (C) 2014 AIP Publishing LLC.

Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2, a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H-2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.

Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters

Solar-driven water splitting to produce hydrogen may be an ideal solution for global energy and environment issues. Among the various photocatalytic systems, platinum has been widely used to co-catalyse the reduction of protons in water for hydrogen evolution. However, the undesirable hydrogen oxidation reaction can also be readily catalysed by metallic platinum, which limits the solar energy conversion efficiency in artificial photosynthesis. Here we report that the unidirectional suppression of hydrogen oxidation in photocatalytic water splitting can be fulfilled by controlling the valence state of platinum; this platinum-based cocatalyst in a higher oxidation state can act as an efficient hydrogen evolution site while suppressing the undesirable hydrogen back-oxidation. The findings in this work may pave the way for developing other high-efficientcy platinum-based catalysts for photocatalysis, photoelectrochemistry, fuel cells and water-gas shift reactions.

Structure and Catalytic Activity of Gold in Low-Temperature CO Oxidation

Structures and catalytic activities of Au thin films supported at anatase TiO(2)(101)) and a Au substrate are studied by using density functional theory calculations. The results show that O(2) can hardly adsorb at flat and stepped Au thin films, even supported by fully reduced TiO(2)(101) that can highly disperse Au atoms and offer strong electronic promotion. Interestingly, in both oxide-supported and pure Au. systems, wire-structured Au can adsorb both CO and O(2) rather strongly, and kinetic analysis suggests its high catalytic activity for low-temperature CO oxidation. The d-band center of Au at the catalytic site is determined to account for the unusual activity of the wire-structured film. A generalized structural model based on the wire-structured film is proposed for active Au, and possible support effects are discussed: Selected oxide surfaces can disperse Au atoms and stabilize the formation of a filmlike structure; they may also serve as a template for the preferential arrangement of Au atoms in a wire structure under low Au coverage.

Effets des nanoparticules manufacturées sur les cellules pulmonaires humaines

La détection et la caractérisation des nanoparticules manufacturées (NPM) est l’une des premières étapes pour contrôler et diminuer leurs risques potentiels sur la santé humaine et l’environnement. Différents systèmes d’échantillonnage dans l’air existent pour l’évaluation d’une exposition aux NPM. Cependant, ils ne mesurent pas le risque potentiel de cette exposition à la santé humaine ni les mécanismes cellulaires qui en seraient responsables. Nos objectifs de recherche sont 1) Évaluer les effets de différents types de nanoparticules sur des cellules pulmonaires humaines et 2) Identifier de nouveaux mécanismes intracellulaires activés lors de l’exposition à divers types de NPM. Méthodologie: La lignée de cellules A549 a été utilisée. Trois types de NPM ont été étudiés (différentes concentrations et temps d’exposition): les nanoparticules de dioxyde de titane de type anatase (TiO2), les nanotubes de carbone simple paroi (NTCSP) et les nanoparticules de noir de carbone (NC). La viabilité cellulaire a été mesurée par le test MTS, le test PrestoBlue et le test d’exclusion du bleu de Trypan (uniquement pour les NTCSP). La mesure du stress oxydatif a été déterminée par la mesure des dérivés réactifs de l’oxygène (ROS) en utilisant l’essai DCFH-DA. L’activation d’une réponse anti-oxydative a été déterminée par la mesure de la forme réduite (GSH) et oxydée (GSSG) du glutathion, ainsi que du ratio GSH/GSSG (seulement avec NTCSP et TiO2). Résultats: Les trois nanoparticules ne semblent pas être toxiques pour les cellules A549 car il y a une diminution significative mais minime de la viabilité cellulaire. Cependant, elles induisent une augmentation du contenu intracellulaire en ROS qui est à la fois dépendante du temps et de la concentration. Aucun changement dans les concentrations de GSH et GSSG n’a été observé. En conclusion, nos données indiquent que la mesure de la viabilité n’est pas un critère suffisant pour conclure à la toxicité des NPM. La production de ROS est un critère intéressant, cependant il faudra démontrer l’activation de systèmes anti-oxydatifs pour expliquer l’absence de mortalité cellulaire suite à l’exposition aux NPM.

Photocatalytic degradation of humic acid in saline waters part 2. Effects of various photocatalytic materials

The present study explores for the first time, the effectiveness of photocatalytic oxidation of. humic acid (HA) in the increasingly important highly saline water. TiO2 (Degussa P25), TiO2 (Anatase), TiO2 (Rutile), TiO2 (Mesoporous) and ZnO dispersions were used as catalysts employing a medium pressure mercury lamp. The effect of platinum loading on P25 and zinc oxide was also investigated. The zinc oxide with 0.3% platinum loading was the most efficient catalyst. The preferred medium for the degradation of HA using ZnO is alkaline, whereas for TiO2 it is acidic. In addition, a comparative study of HA decomposition in artificial seawater (ASW) and natural seawater (NSW) is reported, and the surface areas and band gaps of the catalysts employed were also determined. A spectrophotometric method was used to estimate the extent of degradation of HA. (C) 2003 Elsevier Science B.V. All rights reserved.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

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

Síntese hidrotérmica e caracterização estrutural de titanatos nanotubulares para aplicação na captura do dióxido de carbono

Nanostructured materials have been spreading successfully over past years due its size and unusual properties, resulting in an exponential growth of research activities devoted to nanoscience and nanotechnology, which has stimulated the search for different methods to control main properties of nanomaterials and make them suitable for applications with high added value. In the late 90 s an alternative and low cost method was proposed from alkaline hydrothermal synthesis of nanotubes. Based on this context, the objective of this work was to prepare different materials based on TiO2 anatase using hydrothermal synthesis method proposed by Kasuga and submit them to an acid wash treatment, in order to check the structural behavior of final samples. They were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), adsorption/desorption of N2, thermal analysis (TG/DTA) and various spectroscopic methods such as absorption spectroscopy in the infrared (FT-IR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All the information of characterizations confirmed the complete conversion of anatase TiO2 in nanotubes titanates (TTNT). Observing the influence of acid washing treatment in titanates structure, it was concluded that the nanotubes are formed during heat treatment, the sample which was not subjected to this process also achieved a complete phase transformation, as showed in crystallography and morphology results, however the surface area of them practically doubled after the acid washing. By spectroscopy was performed a discussion about chemical composition of these titanates, obtaining relevant results. Finally, it was observed that the products obtained in this work are potential materials for various applications in adsorption, catalysis and photocatalysis, showing great promise in CO2 capture

Comparison of the nanoparticles performance in the photocatalytic degradation of a styrene-butadiene rubber nanocomposite

Much has been talking about the advantages of polymeric nanocomposites, but little is known about the influence of nanoparticles on the stability of these materials. In this sense, we studied the influence of both oxides of zirconium and titanium, known to have photocatalytic properties, as well as the influence of synthetic clay Laponite on the photodegradation of styrene-butadiene rubber (SBR). SBR nanocomposites were prepared by the colloidal route by mixing commercial polymer lattices and nanometric anatase TiO2, monoclinic ZrO2 or exfoliated Laponite clays colloidal suspensions. To better understand the degradation mechanisms that occur in these nanocomposites, the efficiency of different photocatalysts under ultraviolet radiation was monitored by FT-IR and UV-vis spectroscopies and by differential scanning calorimetric. It was observed that TiO2 and ZrO2 nanoparticles undoubtedly acted as catalysts during the photodegradation process with different efficiencies and rates. However, when compared to pure SBR samples, the polymer degradation mechanism was unaffected. Unlike studies with nanocomposites montmorillonite, exfoliated laponite clay effectively acts as a photostabilizer of polymer UV photodegradation. Copyright © 2012 Wiley Periodicals, Inc.

Generation and characterization of stable, highly concentrated titanium dioxide nanoparticle aerosols for rodent inhalation studies

The intensive use of nano-sized titanium dioxide (TiO2) particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of TiO2 nanoparticles (NP) with biological systems ideally needs to be investigated using physico-chemically uniform and well-characterized NP. In this article, we describe the reproducible production of TiO2 NP aerosols using spark ignition technology. Because currently no data are available on inhaled NP in the 10–50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation studies in rodents. For anticipated in vivo dosimetry analyses, TiO2 NP were radiolabeled with 48V by proton irradiation of the titanium electrodes of the spark generator. The dissolution rate of the 48V label was about 1% within the first day. The highly concentrated, polydisperse TiO2 NP aerosol (3–6 × 106 cm−3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation, and number concentration. Extensive characterization of NP chemical composition, physical structure, morphology, and specific surface area was performed. The originally generated amorphous TiO2 NP were converted into crystalline anatase TiO2 NP by thermal annealing at 950 °C. Both crystalline and amorphous 20-nm TiO2 NP were chain agglomerated/aggregated, consisting of primary particles in the range of 5 nm. Disintegration of the deposited TiO2 NP in lung tissue was not detectable within 24 h.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

Visible light photocatalyst: Iodine-doped mesoporous titania with a bicrystalline framework

Iodine-doped (I-doped) mesoporous titania with a bicrystalline (anatase and rutile) framework was synthesized by a two-step template hydrothermal synthesis route. I-doped titania with anatase structure was also synthesized without the use of a block copolymer as a template. The resultant titania samples were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared, nitrogen adsorption, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible absorption spectroscopy. Both I-doped titania samples, with and without template, show much better photocatalytic activity than commercial P25 titania in the photodegradation of methylene blue under the irradiation of visible light (> 420 nm) and UV-visible light. Furthermore, I-doped mesoporous titania with a bicrystalline framework exhibits better activity than I-doped titania with anatase structure. The effect of rutile phase in titania on the adsorptive capacity of water and surface hydroxyl, and photocatalytic activity was investigated in detail. The excellent performance of I-doped mesoporous titania under both visible light and UV-visible light can be attributed to the combined effects of bicrystalline framework, high crystallinity, large surface area, mesoporous structure, and high visible light absorption induced by I-doping.

Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.