Sol–gel synthesis of porous titania fibers by electro-spinning for water purification

In this study, porous ceramic fibers were prepared by the sol–gel-assisted electro-spinning process using colloidal dispersion of complex fluids for the application of phtotocatalysts. First, polystyrene nanospheres were synthesized by dispersion polymerization as sacrificial templates for porous fibers. Then, the mixture of polyvinylpyrrolidone and the ceramic precursor with the polymeric nanospheres was prepared as the spinning solution and self-organized by electro-spinning, followed by calcination of the electrospun composite fibers. The morphologies of the porous fibers could be controlled according to the size of the templates and the amount of the ceramic precursor. The nano-structure of the pores in the fibrous materials could also be adjusted as open or closed cavities with various potential applications. As a demonstrative application, the macroporous titania fibers could be utilized as photocatalysts for the removal of organic dyes dissolved in water. A better photocatalytic activity of the macroporous fibers with 700-nm pore diameter was observed compared to the result of nonporous titania fibers due to the increased porosity. Collectively, the macroporous ceramic fibers were found to be efficient functional materials to prepare the unique nano-structured materials other than simple nonporous fibers.     

Preparation of porous titania–silica microspheres for treatment of radioactive waste

Titania–silica microspheres have been prepared by sol–gel process. Internal gelation route, which use hexamethylenetetramine as the source of ammonia was used for the preparation spherical gel particles. A cationic surfactant, cetrimide was added in the feed broth for introducing meso-porosity in the gel network. Further paraffin oil emulsion was incorporated in the feed broth before gelation for the formation of larger pores in the gel network. The spherical gel particles thus obtained were washed and heat treated under controlled conditions to remove the entrapped surfactant, paraffin oil and other organic compounds resulting in highly porous intact titania–silica microspheres. The material was characterized by surface area, porosity and by SEM photomicrographs. The ion exchange property of this material was studied using the sorption of plutonium on this material from carbonate medium by distribution coefficient studies and ion exchange column loading and elution experiments.     

Preparation of nanostructured titania thin films by sol–gel technology

This study is concerned with the preparation of hydrolytically active heteroligand complex [Ti(OC₄H₉)_3.61(O₂C₅H₇)_0.39] from titanium butoxide and acetylacetone and with the gel formation kinetics in a solution of this complex upon hydrolysis and polycondensation. Single-layer and double-layer thin films of a solution of this precursor were coated on polished silicon substrates using the dip-coating method. The crystallization of nanostructured titania films during the heat treatment of these xerogel coatings was studied using various protocols; the anatase–rutile phase transition temperature was found to depend on the film thickness. The effects of the precursor solution viscosity on the film thickness and crystallite size were determined.     

Investigation of thermal properties of ruthenium(III) Β-diketonate precursors for preparation of RuO2 films by CVD

By means of a tensimetric flow method and a static method with a silica-membrane zero gauge, the dependence of vapour pressure on temperature was obtained for tris(2,4-pentanedionato)ruthenium(III), Ru(aa)₃, and tris(1,1,1-trifluoropentane-2,4-dionato)ruthenium(III), Ru(tfa)₃. The thermodynamic characteristics of vaporization and sublimation of these complexes were determined. The processes of thermal decomposition of the vapour of the compounds in vacuum, hydrogen and oxygen were investigated by using mass spectrometry in the temperature range 170–550C for Ru(aa)₃ and 150–620C for Ru(tfa)₃. The threshold temperatures of the stability of the vapour of the complexes and the rate constants of the thermolysis processes were determined. The main gaseous products of the thermal decomposition and the dependences of their composition on the presence of hydrogen and oxygen were established.     

Sol–gel derived silver-incorporated titania thin films on glass: bactericidal and photocatalytic activity

Titanium dioxide (TiO₂) and silver-containing TiO₂ (Ag-TiO₂) thin films were prepared on silica pre-coated float glass substrates by a sol–gel spin coating method. The bactericidal activity of the films was determined against Staphylococcus epidermidis under natural and ultraviolet (UV) illumination by four complementary methods; (1) the disk diffusion assay, (2) UV-induced bactericidal test, (3) qualitative Ag ion release in bacteria inoculated agar media and (4) surface topographical examination by laserscan profilometry. Photocatalytic activity of the films was measured through the degradation of stearic acid under UV, solar and visible light conditions. The chemical state and distribution of Ag nanoparticles, as well as the structure of the TiO₂ matrix, and hence the bactericidal and photocatalytic activity, is controlled by post-coating calcination treatment (100–650 °C). Additionally, under any given illumination condition the Ag-incorporated films were found to have superior bactericidal and photocataltyic activity performance compared to TiO₂ thin films. It is shown that with optimized thin film processing parameters, both TiO₂ and Ag-TiO₂ thin films calcined at 450 °C were bactericidal and photocatalytically active.     

Effect of γ-irradiation on the growth of ZnO nanorod films for photocatalytic disinfection of contaminated water

The growth of ZnO nanorods on a flat substrate containing γ-irradiated seeds and their ability to photocatalytically eliminate bacteria in water were studied. The seed layer was obtained, by the spray pyrolysis technique, from zinc acetate solutions γ-irradiated within the range from 0 to 100 kGy. Subsequently, to grow the rods, the seeds were immersed in a basic solution of zinc nitrate maintained at 90 °C. The rate of crystal growth on the seed layer during the thermal bath treatment was kept constant. The resulting materials were characterized morphologically by scanning electron and atomic force microscopies; X-ray diffraction was used to study their morphology and structure and ultraviolet-visible spectroscopy to determine their absorbance. The obtained seed films were morphologically dependent on the radiation dose and this was correlated with the ZnO nanorod films which presented a texture in the (002) direction perpendicular to the substrate. The rods have a hexagonal mean cross section between 20 and 140 nm. Using these rods, the photocatalytic degradation of Escherichia coli bacteria in water was studied; a positive influence of the crystalline texture on the degradation rate was observed.     

Preparation and characterization of perfluorosulfonic resin/titania hybrid transparent films

Preparation and characterization of perfluorosulfonic resin/titania organic-inorganic hybrid films were presented. The transparent hybrid films were prepared by hydrothermal treatment at low temperature of a mixed solution of tetrabutyl titanate and perfluorosulfonic resin with the help of acetylacetone. The characterization was carried out by SEM,XRD,FT-IR,UV-Vis and TGA. The results showed that the perfluorosulfonic resin/titania hybrid transparent films were composed of titania particles dispersed in the perfluorosulfonic resin matrix very well and the titania was of anatase phase. Its diameter de-creased with increasing weight ratio of titania to perfluorosulfonic resin.     

Preparation of titania microfiltration membranes supported on porous Ti–Al alloys

A TiO₂ membrane supported on a planar porous Ti–Al alloy was prepared by combination of electrophoretic deposition and dip-coating. In the electrophoretic deposition process, the membrane thickness increased linearly with the square root of the deposition time, while increased with decrease of the suspension viscosity. The perfect TiO₂/Ti–Al composite membrane was obtained by further dip-coating modification. SEM images showed that the surface of the membrane was defect-free. XRD result indicated that rutile TiO₂ still remained in the membrane bulk as the main phase, while a new phase titanium oxides with the form of Ti_xO_y, where y is less than 2x, was also observed. The supported TiO₂/Ti–Al composite membrane had an average pore size of 0.28 μm, a thickness of 40 μm or so and a pure water flux of 3037 L m⁻² h⁻¹ bar⁻¹.     

Superhydrophilic–superhydrophobic micropattern on TiO2 nanotube films by photocatalytic lithography

The present paper describes an unconventional approach to fabricate the superhydrophilic–superhydrophobic micropatterns on the TiO₂ nanotube structured film by photocatalytic lithography with a two-step process. At the first step, the superhydrophobic TiO₂ nanotube film is fabricated through electrochemical and self-assembled techniques. And at the second step, the superhydrophobic film is selectively exposed to UV light through a photomask to locally photocatalyse the organic monolayer assembled on the TiO₂ nanotube surface. The superhydrophilic–superhydrophobic micropatterns have thus been developed, as a novel template to fabricate a define micropatterned coating of nano octacalcium phosphate by electrochemical deposition. It is indicated that these combined processes reveal a very promising approach for constructing well-defined micropatterns of various functional materials.     

Borrowing titania’s photoinduced electrons for molecular switching

正When exposed to light,titanium dioxide(titania,TiO_2)can act as a powerful catalyst for degrading a variety of organic compounds.Anatase—one of the polymorphs of TiO_2—has a band gap of 3.2 e V;exposing it to ultraviolet light causes the formation of electron-hole pairs,which,in the presence of water,can generate hydroxyl radicals—strong oxidizing agents.The photocatalytic behavior of titania has enabled     

Characterization of porous polyaniline–polystyrenesulfonate composite films using EQCM

Porosity characterization during electrodeposition of polyaniline–polystyrenesulfonate (PA–PSS) in acid solutions has been performed by means of a quartz crystal microbalance (QCM). The quartz crystal impedance analysis was carried out with a new model that takes into account the porosity of the material. PA–PSS films behave as rigid and open porous films, with deposition rates proportional to the previous deposited area. The increment of the area produces dramatic changes on the EQCM response, magnifying the viscous damping of the electrolyte.     

CdS nanoparticles loaded on porous poly-melamine–formaldehyde polymer for photocatalytic dye degradation

CdS nanoparticles were loaded on a highly porous polymer of poly-melamine–formaldehyde (PMF) by a simple co-precipitation approach. Benefiting from the high specific surface area of PMF of 943 m² g^?1, the obtained CdS/PMF composite can adsorb dye molecules efficiently, which favors the subsequent photocatalytic dye degradation process. Typically, 99% of Rhodamine B could be degraded over the optimized CdS/PMF sample after 3 h visible light irradiation. Moreover, the CdS/PMF sample displays reasonable stability during the recycle runs, indicating its potential application for organic pollutants removal by photocatalysis.     

Sol–gel preparation of pure and doped TiO2 films for the photocatalytic oxidation of ethanol in air

Stable sols of TiO₂ were synthesized by a non-aqueous sol–gel process using titanium (IV) isopropoxide as precursor. The microstructure, optical and morphological properties of the films obtained by spin-coating from the sol, and annealed at different temperatures, were investigated using scanning electron microscopy, transmission electron microscopy, diffuse reflectance spectroscopy and ellipsometry. The crystalline structure of the films was characterized by X-ray diffraction and their photocatalytic activity was evaluated for the oxidation of ethanol in air. The influence of the calcination temperature, pre-heat treatment and the number of layers was studied. Simultaneous thermo-gravimetric and differential thermal analysis measurements were carried out to ascertain the thermal decomposition behavior of the precursors. In order to obtain a higher photoresponse in the visible region, a series of vanadium-, niobium- and tantalum-doped TiO₂ catalysts was synthesized by the same sol–gel method. For V doping two different precursors, a vanadium alkoxide and V₂O₅, were used. The effect on the crystallization and photocatalytic activity of the doped TiO₂ films was investigated. Furthermore, to identify the effective composition of the samples, they were characterized by X-ray photoelectron spectroscopy and the surface area of the powders was measured by N₂ adsorption. The 10 wt.% doped catalysts exhibit high photocatalytic activity under visible light and among them the best performance was obtained for the sample containing Ta as dopant. The crystallite sizes are closely related to the photocatalytic activity.     

Engineering the chemistry and nanostructure of porous silicon Fabry-Pérot films for loading and release of a steroid

A method for engineering the surface chemistry and pore dimensions in porous Si films for the purpose of controlling the loading and release of a hydrophobic drug is described. Loading of the steroid dexamethasone is confirmed by Fourier transform infrared spectroscopy, and the release rates are characterized by observation of the appearance of the drug in solution (UV-vis absorption spectroscopy) and by measurement of the Fabry-Perot fringes in the optical reflectivity spectrum of the porous Si film. Optical reflectivity changes provide a measure of the release rate of the drug that is amenable to in-vivo diagnostic applications. Fresh porous Si films are prepared by electrochemical etch and subsequently modified by hydrosilylation with 1-dodecene. The dodecene-modified samples are more robust in aqueous environments and exhibit slower release rates of the drug relative to freshly etched porous Si. Whereas the relatively large dexamethasone molecule is found to infiltrate the freshly etched samples, it does not enter the chemically modified films, because of steric crowding from the dodecyl species. To achieve a high degree of loading into these modified films, the pores are enlarged before hydrosilylation by treatment with an aqueous solution containing HF and dimethyl sulfoxide. The pore expanded, chemically modified samples admit approximately 70% of the dexamethasone that can be admitted into an unmodified (freshly etched) sample. Diffusion of the steroid from the modified, pore expanded films into phosphate-buffered saline solution is slower than from the unmodified sample by a factor of approximately 20, with 90% of the drug delivered in 3 days for the chemically modified films compared to 3 h for the unmodified films.     

Synthesis of lanthanum oxide doped photocatalytic nano titanium oxide through aqueous sol–gel method for titania multifunctional ultrafiltration membrane

An all aqueous sol gel route has been demonstrated for the synthesis of titania multifunctional ultrafiltration membrane on porous alumina substrate. Doping with lanthana was used to increase the thermal stability of anatase phase. This resulted in a nanoporous membrane with considerable percentage of anatase phase even after consolidation at 800°C. The highly homogeneous membranes with a thickness of ~4–5 μm could be observed in SEM. The presence of anatase phase ensured higher photoactivity for the doped membrane compared to the undoped one. The performance of the membrane was tested based on molecular weight cut off and a very high (>90%) filtration efficiency was observed on Bovine Serum Albumin of molecular weight 66 kD. Rejection of 11 nm sized particles points to the uniform nanoporous nature of these highly efficient membranes.     

Role of surface-purity in photocatalytic activity of nanocrystalline anatase–titania processed via polymer-modified sol–gel

Nanocrystalline titania powders have been synthesized via conventional and modified sol–gel using an alkoxide precursor for different R, the ratio of molar concentration of water to that of alkoxide precursor, and calcination temperature. The apparent first-order reaction rate-constant obtained for the powder synthesized via conventional sol–gel is comparable with that of commercial Degussa-P25. Conventional sol–gel has been modified using the hydroxypropyl cellulose polymer to increase the specific surface area of the photocatalyst; and hence, to further enhance its photocatalytic activity. Although higher specific surface area and smaller average nanocrystallite size have been obtained for the powders synthesized via modified sol–gel, they exhibit reduced photocatalytic activity relative to that of powders synthesized via conventional sol–gel. The deactivation of the present photocatalyst has been explained on the basis of reduced surface-purity of the powders after processing via modified sol–gel as induced by the presence of surface-residual organic compounds.