Microcompósitos fotocatalíticos a base de 'Ti' 'O IND.2' modificados com 'Ag'

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UV-stable paper coated with APTES-modified P25 TiO2 nanoparticles

In order to inhibit the photocatalytic degradation of organic material supports induced by small titania (TiO2) nanoparticles, highly photocatalytically active, commercially available P25-TiO2 nanoparticles were first modified with a thin layer of (3-aminopropyl) triethoxysilane (APTES), which were then deposited and fixed onto the surface of paper samples via a simple, dip-coating process in water at room temperature. The resultant APTES-modified P25 TiO2 nanoparticle-coated paper samples exhibit much greater stability to UV-illumination than uncoated blank reference paper. Very little, or no, photo-degradation in terms of brightness and whiteness, respectively, of the P25-TiO2-nanoparticle-treated paper is observed. There are many other potential applications for this Green Chemistry approach to protect cellulosic fibres from UV-bleaching in sunlight and to protect their whiteness and maintain their brightness. © 2014 Elsevier Ltd.

Implications of precursor chemistry on the alkaline hydrothermal synthesis of titania/titanate nanostructures

A systematic study of four parameters within the alkaline hydrothermal treatment of three commercial titania powders—anatase, rutile, and Degussa P25—was made. These powders were treated with 5, 7.5, 9, and 10 M NaOH between 100 and 220 °C for 20 h. The effects of alkaline concentration, hydrothermal temperature, and precursor phase and crystallite size on the resultant nanostructure formation have been studied through X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and nitrogen adsorption. Through the correlation of these data, morphological phase diagrams were constructed for each commercial powder. Interpretation of the resultant morphological phase diagrams indicates that alkaline concentration and hydrothermal temperature affect nanostructure formation independently, where nanoribbon formation is significantly influenced by temperature for initial formation. The phase and crystallite size of the precursor also significantly influenced nanostructure formation, with rutile displaying a slower rate of precursor consumption compared with anatase. Small crystallite titania precursors formed nanostructures at reduced hydrothermal temperatures.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Linkage to chromosome 2q32.2-q33.3 in familial serrated neoplasia (Jass syndrome)

Abstract Causative genetic variants have to date been identified for only a small proportion of familial colorectal cancer (CRC). While conditions such as Familial Adenomatous Polyposis and Lynch syndrome have well defined genetic causes, the search for variants underlying the remainder of familial CRC is plagued by genetic heterogeneity. The recent identification of families with a heritable predisposition to malignancies arising through the serrated pathway (familial serrated neoplasia or Jass syndrome) provides an opportunity to study a subset of familial CRC in which heterogeneity may be greatly reduced. A genome-wide linkage screen was performed on a large family displaying a dominantly-inherited predisposition to serrated neoplasia genotyped using the Affymetrix GeneChip Human Mapping 10 K SNP Array. Parametric and nonparametric analyses were performed and resulting regions of interest, as well as previously reported CRC susceptibility loci at 3q22, 7q31 and 9q22, were followed up by finemapping in 10 serrated neoplasia families. Genome-wide linkage analysis revealed regions of interest at 2p25.2-p25.1, 2q24.3-q37.1 and 8p21.2-q12.1. Finemapping linkage and haplotype analyses identified 2q32.2-q33.3 as the region most likely to harbour linkage, with heterogeneity logarithm of the odds (HLOD) 2.09 and nonparametric linkage (NPL) score 2.36 (P = 0.004). Five primary candidate genes (CFLAR, CASP10, CASP8, FZD7 and BMPR2) were sequenced and no segregating variants identified. There was no evidence of linkage to previously reported loci on chromosomes 3, 7 and 9.

Synthesis of one-dimensional nanocomposites based on alumina nanofibres and their catalytic applications

Materials with one-dimensional (1D) nanostructure are important for catalysis. They are the preferred building blocks for catalytic nanoarchitecture, and can be used to fabricate designer catalysts. In this thesis, one such material, alumina nanofibre, was used as a precursor to prepare a range of nanocomposite catalysts. Utilising the specific properties of alumina nanofibres, a novel approach was developed to prepare macro-mesoporous nanocomposites, which consist of a stacked, fibrous nanocomposite with a core-shell structure. Two kinds of fibrous ZrO2/Al2O3 and TiO2/Al2O3 nanocomposites were successfully synthesised using boehmite nanofibers as a hard temperate and followed by a simple calcination. The alumina nanofibres provide the resultant nanocomposites with good thermal stability and mechanical stability. A series of one-dimensional (1D) zirconia/alumina nanocomposites were prepared by the deposition of zirconium species onto the 3D framework of boehmite nanofibres formed by dispersing boehmite nanofibres into a butanol solution, followed by calcination at 773 K. The materials were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and Fourier Transform Infrared spectroscopy (FT-IR). The results demonstrated that when the molar percentage, X, X=100*Zr/(Al+Zr), was > 30%, extremely long ZrO2/Al2O3 composite nanorods with evenly distributed ZrO2 nanocrystals formed on their surface. The stacking of such nanorods gave rise to a new kind of macroporous material without the use of any organic space filler\template or other specific drying techniques. The mechanism for the formation of these long ZrO2/Al2O3 composite nanorods is proposed in this work. A series of solid-superacid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid superacid counterparts were characterised by a variety of techniques including 27Al MAS-NMR, SEM, TEM, XPS, Nitrogen adsorption and Infrared Emission Spectroscopy. NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained superacids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia. Preparation of hierarchically macro-mesoporous catalyst by loading nanocrystallites on the framework of alumina bundles can provide an alternative system to design advanced nanocomposite catalyst with enhanced performance. A series of macro-mesoporous TiO2/Al2O3 nanocomposites with different morphologies were synthesised. The materials were calcined at 723 K and were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscope (TEM), N2 adsorption/desorption, Infrared Emission Spectroscopy (IES), and UV-visible spectroscopy (UV-visible). A modified approach was proposed for the synthesis of 1D (fibrous) nanocomposite with higher Ti/Al molar ratio (2:1) at lower temperature (<100oC), which makes it possible to synthesize such materials on industrial scale. The performances of a series of resultant TiO2/Al2O3 nanocomposites with different morphologies were evaluated as a photocatalyst for the phenol degradation under UV irradiation. The photocatalyst (Ti/Al =2) with fibrous morphology exhibits higher activity than that of the photocatalyst with microspherical morphology which indeed has the highest Ti to Al molar ratio (Ti/Al =3) in the series of as-synthesised hierarchical TiO2/Al2O3 nanocomposites. Furthermore, the photocatalytic performances, for the fibrous nanocomposites with Ti/Al=2, were optimized by calcination at elevated temperatures. The nanocomposite prepared by calcination at 750oC exhibits the highest catalytic activity, and its performance per TiO2 unit is very close to that of the gold standard, Degussa P 25. This work also emphasizes two advantages of the nanocomposites with fibrous morphology: (1) the resistance to sintering, and (2) good catalyst recovery.

Immobilised anatase on clay mineral particles as a photocatalyst for herbicides degradation

Materials consisting of anatase linked to Laponite particles were synthesized by the reaction of TiOSO4 with Laponite, and were used for the degradation of pesticides. All these materials were characterized by XRD, FTIR, Raman, TEM, specific surface area and porosity determinations. Based on the amount of photoactive phase per unit mass of the clay mineral, not based on the total weight of the catalysts, these porous catalysts were displaying a high degradation rate than commercial P25. The TiO2 immobilized clay mineral catalysts can sediment in few minutes and could be readily separated out from a slurry system after the photocatalytic reaction. Settling properties of these catalysts are enormously high in aqueous media in contrast to P25.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

Painting anatase (TiO2) nanocrystals on long nanofibers to prepare photocatalysts with large active surface for dye degradation and organic synthesis

Anatase TiO2 nanocrystals were painted on H-titanate nanofibers by using an aqueous solution of titanyl sulfate. The anatase nanocrystals were bonded solidly onto the titanate fibers through formation of coherent interfaces at which the oxygen atoms were shared by the nanocrystals and the fiber. This approach allowed us to create large anatase surfaces on the nanofibers, which are active in photocatalytic reactions. This method was also applied successfully to coat anatase nanocrystals on surfaces of fly ash and layered clay. The painted nanofibers exhibited a much higher catalytic activity for the photocatalytic degradation of sulforhodamine B and the selective oxidation of benzylamine to the corresponding imine (with a product selectivity >99%) under UV irradiation than both the parent H-titanate nanofibers and a commercial TiO2 powder, P25. We found that gold nanoparticles supported on H-titanate nanofibers showed no catalytic activity for the reduction of nitrobenzene to azoxybenzene, whereas the gold nanoparticles supported on the painted nanofibers and P25 could efficiently reduce nitrobenzene to azoxybenzene as the sole product under visible light irradiation. These results were different from those from the reduction on the gold nanoparticles photocatalyst on ZrO2, in which the azoxybenzene was the intermediate and converted to azobenzene quickly. Evidently, the support materials significantly affect the product selectivity of the nitrobenzene reduction. Finally, the new photocatalysts could be easily dispersed into and separated from a liquid because of their fibril morphology, which is an important advantage for practical applications.

Translocation of bats as a conservation strategy : previous attempts and potential problems

Translocation is an increasingly popular conservation tool from which a wide range of taxa have benefited. However, to our knowledge, bats have not been translocated successfully. Bats differ behaviourally, morphologically and physiologically from the taxa for which translocation the- ory has been developed, so existing guidelines may not be directly transferable. We review previous translocations of bats and discuss characteristics of bats that may require special consideration dur- ing translocation. Their vagility and homing ability, coloniality, roost requirements, potential ability to transmit diseases, susceptibility to anthropomorphic impacts, and cryptic nature have implications for establishing populations, effects of these populations on the release site, and ability to monitor translocation success following release. We hope that our discussion of potential problems will be able to supplement the existing, more generic guidelines to provide a starting point for the planning of bat translocations.

Revisiting the CO oxidation reaction on various Au/TiO2catalysts: Roles of the surface OH groups and the reaction mechanism

This work aims to understand the influence of TiO2 surface structure in Au/TiO2 catalysts on CO oxidation. Au nanoparticles (3 wt%) in the range of 4 to 8 nm were loaded onto four kinds of TiO2 surfaces, which had different surface structures and were synthesized by calcining hydrogen titanate nanotubes at various temperatures and in different atmospheres. The Au catalyst supported on anatase nanorods exhibited the highest activity in CO oxidation at 30 °C among all the five Au/TiO2 catalysts including the reference catalyst of Au/TiO2-P25. X-ray photoelectron spectroscopy (XPS) and infrared emission spectra (IES) results indicate that the anatase nanorods have the most active surface on which water molecules can be strongly adsorbed and OH groups can be formed readily. Theoretical calculation indicates that the surface OH can facilitate the O2 adsorption on the anatase surface. Such active surface features are conducive to the O2 activation and CO oxidation

Photocatalytic and Thermal Degradation of Poly(methyl methacrylate), Poly(butyl acrylate), and Their Copolymers

The photocatalytic and thermal degradations of poly(methyl methacrylate), poly(butyl acrylate), and their copolymers of different compositions were studied. The photocatalytic degradation was investigated in o-dichlorobenzene in the presence of two different catalysts, namely, Degussa P-25 and combustion synthesized nanotitania (CSN-TiO2). The samples were analyzed by using gel permeation chromatography (GPC) to obtain the molecular weight distributions (MWDs) as a function of reaction time. Experimental data indicated that the photodegradation of these polymers occurs by both random and chain end scission. A continuous distribution kinetic model was used to determine the degradation rate coefficients by fitting the experimental data with the model. Both the random and specific rate coefficients of the copolymers decreased with increasing percentage of butyl acrylate (BA). Thermal degradation of the copolymers was investigated by thermo-gravimetry. The normalized weight loss profiles for the copolymers showed that the thermal stability of the copolymers increased with mole percentage of BA in the copolymer (PMMABA). The Czawa method was used to determine the activation energies at different conversions. At low acrylate content in the copolymer, the activation energy depends on conversion, indicating multiple degradation mechanisms. At high acrylate content in the copolymer, the activation energy is independent of conversion, indicating degradation by a one-step mechanism.

Nutrient levels in experimental tanks supplied with prawn pond effluent: the effect of artificial substrate and different densities of the banana prawn Penaeus merguiensis (de Man)

To experimentally investigate the effect of vertical artificial substrate and different densities of the banana prawn Penaeus (Fenneropenaeus) merguiensis on nutrient levels in prawn pond effluent, a time series experiment was conducted in a replicated tank system supplied periodically with discharge from a prawn production pond. Few differences (P>0.05) were detected between tanks without prawns, and tanks with low densities (5 prawns in 1700 litres) of prawns (10-12 g), in terms of nitrogen and phosphorus in the water column over the 28-day experimental period. Higher densities of prawns (starting at 25 or 50 per tank) caused an elevation of these macronutrients in the water column. This was partly due to prawn biomass losses from mortalities and weight reductions in the tank system. The survival and condition of prawns was significantly (P<0.05) reduced in tanks at these higher densities. The presence of artificial substrate (2 m2 tank-1) did not affect (P>0.05) the levels of nutrients in tank water columns, but significantly (P<0.05) increased the amount of nitrogen in tank residues left at the end of the trial when no prawns were present. The prawns had obviously been grazing on surfaces inside the tanks, and their swimming actions appeared to keep light particulate matter in suspension. Higher prawn densities increased microalgal blooms, which presumably kept ammonia levels low, and it is suggested that this association may provide the means for improved remediation of prawn farm effluent in the future.