Enhanced photocatalytic activity of Au-buffered TiO2 thin films prepared by radio frequency magnetron sputtering

Au-buffered TiO₂ thin films have been prepared by radio frequency magnetron sputtering method. The structural and morphological properties of the thin films were characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic activity of the samples was evaluated by the photodecomposition of methylene blue. The Au-buffer thin layer placed between the TiO₂ thin films significantly enhanced photocatalytic activity by 50%. Annealing the Au-buffered TiO₂ thin film at 600 °C decreased the film roughness, but it increased the surface area and anatase crystalline size, enhancing the photocatalytic activity.     

Wetting angles and photocatalytic activities of illuminated TiO2 thin films

TiO₂ thin films have been prepared by physical vapour deposition (PVD) and plasma enhanced chemical vapour deposition (PECVD) to study the UV-induced photo-activity of this material. Wetting angle variations and photo-catalytic activity for the degradation of dyes upon UV illumination have been compared for thin films with different crystalline structure (amorphous, rutile and anatase), microstructure (columnar, compact, etc.) and porosities as estimated from the values of their refraction indices and their direct assessment with a quartz crystal monitor. The surface of the thin films became superhydrophilic upon UV light irradiation and then it recovered its original state by keeping the samples in the dark. Wetting angle decays follow very similar kinetics for amorphous and crystalline films, independently of their actual porosities. By contrast the photo-catalytic activity was very dependent on the crystalline structure of the films (anatase > rutile > amorphous) and on their porosities. The different behaviour depicted by the films with regard to these two properties suggests that they respond to different though related mechanisms and that they cannot be considered as equivalent when trying to prove the photo-activity of TiO₂.     

Simultaneous improvement of photocatalytic and superhydrophilicity properties of nano TiO2 thin films

Anatase TiO₂ nano thin films were prepared on glass substrates by sol–gel dip coating method using Tween-80 as a surfactant, TiCl₄ as the Ti precursor, and ethanol as a solvent. Atomic force microscopy, X-ray diffraction, and UV–Vis. photospectrometery experiments were performed to analyze the surface, structural and optical characteristics of the films. The effects of chemical aging time on the morphology, photocatalytic and superhydrophilicity behaviors of the films were studied. We show there is an optimum aging time at 2 h which photocatalytic and superhydrophilicity properties are at their maximum values simultaneously. This is useful in the self-cleaning industry.     

Dopant-free, polymorphic design of TiO2 nanocrystals by flame aerosol synthesis

A dopant-free aerosol synthesis of highly crystalline TiO₂ nanoparticles (20–35 nm) with tunable polymorphic content is demonstrated by rapid flame spray pyrolysis. By controlling precisely the total ambient oxygen partial pressure of the combustion in a quartz tube enclosure, anatase content as high as 96 wt% (4 wt% rutile) was obtained at high oxic flame conditions, while rutile content as high as 94 wt% (6 wt% anatase) was obtained under anoxic flames. The polymorphic variability lies within a narrow range of combustion equivalence ratios, that is, 1.0<Φ<1.5. Unlike any other flame aerosol syntheses, the anatase and rutile crystallite sizes were similar within each sample. Under highly oxic flame conditions (Φ<1.0), twinnings between anatase {0 1 1} planes could be observed, inferring oriented attachment taking place. Such mechanism could not, however, be seen under anoxic flame (Φ>1.0) possibly due to physical hindrance by surface carbonaceous content (typically <2 wt%). The carbon content can be easily removed by short calcination without significantly affecting the surface areas and crystallite properties of the original TiO₂ nanocrystals, preserving hence its pristine state.     

Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor

Amorphous TiO₂, prepared at room temperature through a sol–gel method implementing hydrolysis of TiCl₄, has been supported on graphite rods and then annealed at 673 K. In this way graphite was completely covered by a porous anatase TiO₂ layer, with an external thickness of about 1 μm, with graphite pores completely filled by the semiconductor particles. The obtained electrode was structurally characterized by SEM microscopy coupled to EDAX mapping and by Raman spectroscopy. A Pyrex annular reactor was designed in order to test the prepared electrodes for the photoelectrocatalytic degradation of 4-nitrophenol, a target pollutant dissolved in aqueous conductive solution. The continuous reactor worked in total recirculation mode and the degradation runs were carried out by applying near UV-light, bias or both energy sources. The influence of flow rate, initial 4-nitrophenol concentration and applied potential on the degradation rate was studied.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Preparation and characterization of CeO2/TiO2 nanoparticles by flame spray pyrolysis

Nanocrystalline TiO₂, CeO₂ and CeO₂-doped TiO₂ have been successfully prepared by one-step flame spray pyrolysis (FSP). Resulting powders were characterized with X-ray diffraction (XRD), N₂-physisorption, Transmission Electron Microscopy (TEM) and UV-Vis spectrophotometry. The TiO₂ and CeO₂-doped TiO₂ nanopowders were composed of single-crystalline spherical particles with as-prepared primary particle size of 10-13 nm for Ce doping concentrations of 5-50 at%, while square-shape particles with average size around 9 nm were only observed from flame-made CeO₂. The adsorption edge of resulting powder was shifted from 388 to 467 nm as the Ce content increased from 0 to 30 at% and there was an optimal Ce content in association with the maximum absorbance. This effect is due to the insertion of Ce^3+/4+ in the TiO₂ matrix, which generated an n-type impurity band.     

Preparation of UO2/TiO2 composite ceramic fuel by sol gel-press forming method

This paper studies the preparation of UO₂/TiO₂ composite ceramic fuel through sol gel-press forming. The research shows that at 1200–1300 °C, UO₂/TiO₂ composite ceramic grains are small, uniform and compact. Among them, UO₂–0.5 wt%TiO₂ has the highest density and good mechanical strength at 1250 °C.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Efficiency improvement of dye-sensitized solar cells based on electrodeposited TiO2 films by low temperature post-treatment

Porous crystalline TiO₂ films can be prepared at low temperatures (80 °C) by surfactant-assisted electrodeposition from TiCl₃ solution. Nevertheless, up to now calcination at high temperatures (typically 450 °C) was still necessary to establish a good performance of these films in dye-sensitized solar cells (DSSC). With this study we report that water vapour treatment at much lower temperatures (150 °C) for 1 week improves the performance of the films in DSSC to the same degree as calcination although the overall crystallinity remains lower. Reason for the good efficiency is that the porous structure stays intact and thus the dye molecules can be better adsorbed. Avoiding high temperatures during the preparation process of TiO₂ films for the application in DSSC enables the use of polymer substrates for the fabrication of flexible solar cells.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Preparation and electrochemical capacitance of RuO2/TiO2 nanotubes composites

In this paper, RuO₂/TiO₂ nanotubes composites were synthesized by loading various amounts of RuO₂ on TiO₂ nanotubes. The symmetric supercapacitors based on these nanocomposites were fabricated by using gel polymer PVA-H₃PO₄-H₂O as electrolyte. The electrochemical capacitance performance of the nanocomposites in these supercapacitors was investigated by current-potential responses, galvanostatic charge-discharge tests and electrochemical impedance spectroscopy. The results show that the three dimensional nanotube network of TiO₂ offers a solid support structure for active materials RuO₂, allows the active material to be readily accessible (available) for electrochemical reactions, and improves the efficiency of the active materials. A maximum specific capacitance of 1263 F/g was obtained for the RuO₂ which was loading on TiO₂ nanotubes.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.     

Preparation of porous TiO2 by a novel freeze casting

Highly porous and open interconnected pore structural TiO₂ were prepared by a novel freeze casting method. In the experiment, the well-dispersed aqueous slurries were first frozen, and then dried at a reduced vacuum. Since the sublimation of ice crystals developed in the freezing process, the green bodies with highly porous were obtained. The phase composition and the microstructure of the sintered samples were characterized by XRD, SEM, porosity and the pore size distribution was measured by mercury porosimetry. The results demonstrated that the PVA concentration in the slurries remarkably affect the microstructure of TiO₂ ceramics. The pore morphology of TiO₂ ceramics with 3 wt.% polyvinyl alcohol (PVA) addition was dendritic, and however, the pore morphology of TiO₂ ceramics with 6 wt.% PVA addition changed into columnar. The reason for the variation of the pore morphology was ascribed to the effect of the PVA gelation on the growth behavior of the ice crystals.     

Photocatalytic activity of transparent porous glass supported TiO2

A porous glass tube with a composition of 96SiO₂·4B₂O₃ (wt%) supported TiO₂ shows high photooxidation activity due to its transparency and large surface area. The surface area of the porous glass tube supported TiO₂ is 10,000 times larger than that of conventional materials. TiO₂ crystals supported are anatase type. Transparency of the porous glass tube is very important. Herein, sol–gel and chemical vapor deposition (CVD) processes were employed as TiO₂ supporting processes. CVD process is more effective. For instance, an aqueous methylene blue solution with 1 ppm concentration almost thoroughly decomposes at a contact time of 300 s using porous glass tube supported TiO₂ prepared by CVD process under irradiating with 10 W low-pressure mercury lamp, on the other hand, opaque porous alumina tube supported TiO₂ was only 25%. The smaller the pore size of the porous glass tube, the larger the transparency and the permeation resistance through porous glass tube. Hence, porous glass tube with ca. 40 nm pore diameter is suitable from the standpoint of a practical use.     

Operando FTIR study of the photocatalytic oxidation of acetone in air over TiO2–ZrO2 thin films

Operando FTIR spectroscopy has been used to study the photocatalytic oxidation of acetone vapors over semiconductors films containing TiO₂ and ZrO₂. Preparation of these coatings was carried out by dipping a silicon wafer in stable sols containing particles of TiO₂, Ti_1−xZr_xO₂, or a mixture of ZrO₂ and TiO₂. These differences in chemical composition and phase homogeneity were selected in order to determine their effect on the photocatalytic performance. A transmission cell specifically designed for in situ studies of photocatalytic coatings was utilized for the FTIR experiments under reaction conditions. In contrast with investigations with powdered photocatalysts, the use of thin films guarantees that the whole semiconductor is irradiated, and for that reason purely photochemical reactions are monitored. Acetone adsorption takes place molecularly and is higher on the Ti_1−xZr_xO₂ coating. This fact is very likely related to the higher specific surface of the samples containing Zr. However, the maximum photocatalytic rate for acetone degradation corresponds to the films composed by a binary mixture of TiO₂ and ZrO₂. On the other hand, remarkable differences on the type and concentration of intermediates appearing as a result of the photocatalytic oxidation of acetone are found for the coatings studied. A simple kinetic model was applied to analyze the evolution of both gas phase and surface species. The parameters obtained indicate that each specific surface process is affected in a different way by the variation in the composition of the photoactive films.     

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO₂ thin films were fabricated. The Ag/TiO₂ composite films were prepared by incorporating Ag in the pores of TiO₂ films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N₂ adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy. The antibacterial activities of the composite films were studied by a fluorescence label method using Escherichia coli (E. coli) as a model. The as-prepared mesoporous TiO₂ films showed much higher antimicrobial efficiency than that of glass and commercial P25 TiO₂ spinning film. The facts would result from the high surface area, small crystal size and more active sites for the mesoporous catalysis. After the doping of Ag, a significant improvement for the antimicrobial ability was obtained. To elucidate the roles of the membrane photocatalyst and the doped silver in the antimicrobial activity, cells from a silver-resistant E. coli were used. These results indicated that Ag nanoparticles in the mesoporous were not only an antimicrobial but also an intensifier for photocatalysis. The as-prepared mesoporous composite film is promising in application of photocatalysis, antimicrobial and self-clean technologies.     

Preparation of highly stable superhydrophobic TiO2 surfaces with completely suppressed photocatalytic activity

TiO₂ nanoparticles with a mean size of 20–30 nm were covered by ultrathin polydimethylsiloxane (PDMS) film, which shows hydrophobic properties. Surfaces consisting of the PDMS-coated TiO₂ particles showed water contact angles close to 170°. In contrast to the hydrophobic films consisting of organic molecules, which can be photocatalytically decomposed on TiO₂ in the presence of UV light, PDMS-coating on TiO₂ was highly stable. The PDMS-coating completely suppressed the photocatalytic activity of TiO₂. The unique properties of PDMS-coating can be exploited for UV protection layer and self-cleaning surfaces.