AUGMENTATION OF PHOTOCATALYTIC ACTIVITY OF TiO2 THIN FILMS PREPARED BY A SOL-GEL TECHNIQUE

In order to increase the photocatalytic activity on TiO₂ thin film per its external surface area, the structure of flat thin film was modified by adding a small amount of polyethylene glycol (PEG) to TiO₂ sol solution. By firing PEG contained in a TiO₂ gel film, a porous structure was developed. The photocatalytic activities of the thin films prepared thus were evaluated by the degradation of 2-propanol in the aqueous solutions under black light illumination. The photocatalytic activity of TiO₂ thin film prepared with added PEG 400 by 2.6 wt% or PEG 2000 by 9.5 wt% was increased by about 30% as compared to that prepared without added PEG.     

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.     

Synthesis, characterization and photocatalytic properties of sol-gel TiO2 films

The application of heterogeneous photocatalysis is described as an advanced oxidation process (AOP) for the degradation of the diazo reactive dye using immobilized TiO₂ as a photocatalyst. Starting TiO₂ solutions were prepared with and without the addition of polyethylene glycol (PEG) and TiO₂ films were directly deposited on a borosilicate glass substrate using the sol-gel dip-coating method. The surface morphology and the nanoscale roughness of TiO₂ films were studied by means of atomic force microscopy (AFM). Structural properties of TiO₂ were identified by X-ray diffraction (XRD). The decomposition behaviour of organic compounds from the gels was investigated using thermal gravimetry (TG) and differential scanning calorimetry (DSC). Photocatalytic activities of TiO₂ films in the process of degradation of the commercial diazo textile dye Congo red (CR), used as a model pollutant, were monitored by means of UV/vis spectrophotometry. The kinetics of the degradation of the CR dye was described with the Langmuir-Hinshelwood (L-H) kinetic model.The addition of PEG to the TiO₂ solution resulted in the changes in the film surface morphology, and affected the ratio of anatase-rutile crystal phases and the photocatalytic activity of TiO₂. The TiO₂ film prepared with PEG is characterized by higher roughness parameters (R_a, R_max, R_q, R_z and Z_max), a lower amount of the rutile phase of TiO₂, a higher amount of the anatase phase of TiO₂ and a better photocatalytic activity compared to the TiO₂ film without the addition of PEG.     

Superhydrophilic Cu-doped TiO2 thin film for solar-driven photocatalysis

Nanosized Cu-doped TiO₂ film was prepared by the sol–gel spin coating technique. XPS analysis showed that Cu atoms had been successfully doped into TiO₂ lattice, which hence modified the surface chemical composition. As a result, the Cu-doped TiO₂ thin film possessed a superhydrophilic surface with a water contact angle (WCA) only 5.1° and exhibited excellent anti-fogging behavior. The Cu-doped TiO₂ thin film also exhibited a much better photocatalytic activity than the reference TiO₂ thin film, as evaluated by the degradation of 10 mg/L methylene blue (MB) solution under simulated solar-driven irradiation.     

Influence of Metal (Au, Ag) Micro-Grid on the Photocatalytic Activity of TiO2 Film

In this paper, we prepared TiO₂ thin film with the surface modified by a connected Au micro-grid via a microsphere lithography strategy, and the modified films show higher photocatalytic activity than the pure TiO₂ film. The photocatalytic activity improved as Au loading increased, obtaining the best performance at a certain loading amount, and then decreased at higher loading amount. This behavior, not observed in TiO₂ films modified with Ag micro-grid, can be attributed to the relationship between the energetic positions and the metal clusters size.     

Photocatalytic Decomposition of Formic Acid Under Visible Light Irradiation Over V-ion-implanted TiO2 Thin Film Photocatalysts Prepared on Quartz Substrate by Ionized Cluster Beam (ICB) Deposition Method

Unique visible-light-responsive TiO₂ photocatalysts (λ>450 nm) were successfully developed by implantation of V ions into the TiO₂ thin films prepared on a quartz substrate by an ionized cluster beam (ICB) deposition method. After V ions implantation into TiO₂ thin film, the photocatalytic activity of the thin films for the decomposition of formic acid into CO₂ and H₂O was found to proceed efficiently under visible light irradiation longer than 450 nm. The TiO₂ thin film photocatalysts were characterized by XRD, UV-vis, XPS, FE-SEM and AFM.     

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.     

A novel deposition precipitation method for preparation of Ag-loaded titanium dioxide

Ag/TiO₂ photocatalysts were prepared by a novel deposition precipitation method. Formation of Ag nanoparticles on the surface of TiO₂ was confirmed by XRD, HRTEM and XPS. The photocatalytic activity of Ag/TiO₂ was tested with the photocatalytic degradation of methyl orange and found effectively enhanced. The optimum content of Ag for photocatalytic activity is about 2.0 wt%.     

Enhanced photocatalytic activity of highly transparent superhydrophilic doped TiO2 thin films for improving the self-cleaning property of solar panel covers

Undoped and metal doped nanocrystalline TiO₂ transparent thin films were synthesized on glass substrates via sol-gel/dip-coating method. TiO₂ thin film coatings can be applied to the surfaces of solar panels to impart self-cleaning properties to them. The structural and optical properties of few nanometer-thick films were characterized by XRD, SEM, CA, AFM, XPS, and UV–Vis spectrophotometry techniques. The stoichiometric TiO₂ films crystallized in anatase phase, with a particle size of ～100 nm, which were uniformly distributed on the surface. The prepared films with a roughness of ～1–5 nm, increased the hydrophilicity of the glass surface. Reducing the amount of Ti precursor (X) favored the improvement of film quality. To improve the photocatalytic activity of the TiO₂ thin film, it was doped with Ni, Cd, Mo, Bi and Sr metal ions. The effect of metal doping on the photocatalytic activity of the films was investigated using the degradation process of methylene blue (MB) dye as the model contaminant. Among the prepared coatings, the Sr–TiO₂ film showed the highest efficiency for MB degradation. It increased the dye degradation efficiency of the films under both UV and Vis lights. The kinetic investigations also showed that the degradation of MB by TiO₂ and M ? TiO₂ films obeyed the pseudo-first order kinetics.     

Photochemical diodes of a TiO2 film prepared by a sol-gel method

Photochemical diodes were prepared using a thin film of TiO₂ made from titanium isopropoxide by a sol-gel method. A half part of a conductive SnO₂ film plated on a quartz plate was coated with the TiO₂ film, and the other parts of the SnO₂ substrate were coated with a thin Pt film. The photochemical diode thus prepared shows photocatalytic activity for hydrogen evolution from aqueous ethanol solutions containing NaOH or HClO₄. No other products are detected in the gas phase. Hydrogen evolution from the Pt part is definitely observed, indicating electron transfer from the TiO₂ film to the Pt film through the SnO₂ film. Another type of photochemical diode, the TiO₂ film coated on a Pt plate, is found to show higher activity than the TiO₂/SnO₂/Pt device for the hydrogen photo-evolution without any support electrolyte. Hydrogen evolution on this device, however, occurs on the TiO₂ side but not on the Pt side. These results are discussed in terms of a photo-electrochemical mechanism at semiconductor surfaces.     

Preparation, crystal structure, and photocatalytic activity of TiO2 films by chemical vapor deposition

Photocatalytic activities of TiO₂ films were experimentally studied. TiO₂ films with different crystal structures (amorphous, anatase, rutile) were prepared by a Low Pressure Metal Organic Chemical Vapor Deposition (LPMOCVD) at different reaction temperatures and also by a Sol-Gel method using TTIP (Titanium Tetra Iso-Pro-poxyde). The Effect of CVD preparation method, CVD reaction conditions, crystal structure and wave-length of UV light on the photocatalytic decomposition rate of methylene blue in aqueous solution were studied. First, the characteristics of CVD preparation of TiO₂ films, such as the CVD film growth rate, crystal structure and morphology of the grown TiO₂ films, were experimentally studied as a function of CVD reaction temperature. Secondly, photocatalytic activities of TiO₂ films were evaluated by using two types of photo-reactors. The results indicated that TiO₂ films prepared by CVD exhibit higher photocatalytic activity than a catalyst prepared by the Sol-Gel method. Among the CVD grown TiO₂ films, anatase and rutile showed high photocatalytic activities. However, amorphous TiO₂ films showed lower activities. The activity of the photocatalysts of anatase films was excellent under all types of UV-lamps. The activity of CVD-prepared anatase films was four to seven times higher than that of photocatalyst films prepared by the Sol-Gel method.     

Flexible TiO2 nanograss array film decorated with BiOI nanoflakes and its greatly boosted photocatalytic activity

A flexible TiO₂ nanograss array film on Ti wire mesh was prepared by a mild chemical reaction. To overcome its shortcoming of almost no absorption of visible light, successive ionic layer adsorption and reaction (SILAR) was executed to decorate the prepared TiO₂ film with BiOI. The results of XRD and SEM measurements showed that BiOI nanoflakes formed on the surface of TiO₂ film, and the loading amounts of BiOI nanoflakes increased with the increase in SILAR cycles. The XPS results confirmed the heterojunction formation of BiOI-TiO₂. The photocurrent measurement suggests that a moderate loading amount of BiOI nanoflakes is beneficial to improve the charge separation efficiency, which is ascribed to the heterojunction formation of BiOI-TiO₂. The BiOI-decorated TiO₂ film with SILAR cycles of seven showed the most excellent visible-light photocatalytic activity among all the samples. Compared with the bareTiO₂ nanograss array film, its visible-light photocatalytic activity increased by 11.7 times. The flexible BiOI-decorated TiO₂ nanograss array film with high photocatalytic activity shows great applications in air pollution and the pollution caused by offshore oil spills.     

LIQUID-PHASE PHOTOCATALYTIC REACTION ON TiO22 THIN FILM

The photocatalytic decomposition process on TiO₂ thin films, was modeled by taking the decay of illumination intensity via Lambert-Beer law into account. For the sake of experimental verification of the proposed model, Ti02 thin films were prepared on a glass substrate by a dip-coating method combined with a sol-gel process and the photocatalyuc activity of the thin films was evaluated by the decomposition of 2-propanol (IPA) in an aqueous solution under illumination of UV light source. The film thickness up to 1.4 μm increased with the withdrawal speed raised to the power 0.6 and was proportional to the number of application (i.e., repetition of dip-coating process). The TiO₂ gel films prepared by a dip-coating technique, were subject to firing at 500°C. The photocatalytic decomposition rate could be expressed apparently as first-order with respect to IPA concentration. The observed relationship between apparent first-order rate constant of decomposition and the film thickness could satisfactorily be explained by the proposed model.     

Photo-Generated Activities of Nanocrystalline TiO<Subscript>2</Subscript> Thin Films

Transparent nanocrystalline TiO₂ thin films with high photocatalytic activity and photo-induced wettability were successfully deposited on a glass slide. Crystal phase transformations and particle size of TiO₂ were investigated. Structural and morphological properties of the films were investigated. The photocatalytic activity of the TiO₂ films was evaluated. It is found that the photocatalytic activity of TiO₂ thin films is significantly decreased by increasing the annealing temperature, which results in a decrease in BET surface area and an increase in crystal size. In addition, increasing film thickness within a certain range significantly improves the photocatalytic activity without causing crack formation of the TiO₂ films. Photocatalytic oxidation and photo-induced wettability conversion on the films were investigated. It is found that photo-induced hydrophilic conversion is observed even on the samples annealed at high temperature. The best photo-generated activities are obtained by optimization of dip-coating cycles and annealing temperatures.     

Preparation,characterization and photocatalytic activity of a novel nanostructure composite film derived from nanopowder TiO2 and sol–gel process using organic dispersant

A novel sol–gel-derived titanium dioxide nanostructure composite has been prepared by spin-coating and investigated for the purpose of producing films. The processing of the composite sol–gel photocatalysts involved utilizing of precalcinated nanopowder titanium dioxide as filler mixed with sol and heat treated. The sol solution was prepared by adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl 35.5% (mole ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10), then a solution of 2 wt% methylcellulose was added and stirred at room temperature. Precalcinated TiO₂ nanopowder was dispersed in the sol and the prepared mixture was deposited on the microscope glass slide by spin-coating. The inhomogeneity problem in preparation of composite film which causes peeling off and cracking after calcination due to the shrinkage of the films with thermal treatment were overcome by using methylcellulose (MC) as a dispersant. The composite heat treated at approximately 500 °C has the greatest hardness value. Surface morphology of composite deposits by scanning electron microscopy (SEM) showed remarkable increase in the composite surface area. Evaluation of the adhesion and bonding strength between the coating and substrate was carried out by the scratch test technique. The minimum load which caused the complete coating removal, for composite thick film was 200 g/mm² which indicates a strong bond to the substrate. Photocatalytic activity of the composite film was evaluated through the degradation of a textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) as a model pollutant and were compared with those of similar composite thick film without MC, thin film of TiO₂ and TiO₂ nanopowder. The results show that the photocatalytic activity and stability of the composite films are higher than those of nanopowder TiO₂. However, a remarkable increase in the composite surface and good mechanical integrity make this composite film a viable alternative for commercial applications.     

Enhanced Solid‐Phase Photocatalytic Degradation Activity of a Poly(vinyl chloride)‐TiO2 Nanocomposite Film with Bismuth Oxyiodide

A new type of photodegradable poly(vinyl chloride)‐bismuth oxyiodide/TiO₂ (PVC‐BiOI/TiO₂) nanocomposite film was prepared by embedding a nano‐TiO₂ photocatalyst modified by BiOI into the commercial PVC plastic. The solid‐phase photocatalytic degradation behavior of the as‐prepared film was investigated in ambient air at room temperature under UV light irradiation, with the aid of UV‐Vis spectroscopy, weight loss monitoring, scanning electron microscopy, and FT‐IR spectroscopy. Compared to the PVC‐TiO₂ nanocomposite film, the PVC‐BiOI nanocomposite film and the pure PVC film, the PVC‐BiOI/TiO₂ nanocomposite film exhibited a higher photocatalytic degradation activity. The optimal mass ratio of BiOI to TiO₂ was found to be 0.75 %. The weight loss rate of the PVC‐BiOI/TiO₂ nanocomposite film reached 30.8 % after 336 h of irradiation, which is 1.5 times higher than that of the PVC‐TiO₂ nanocomposite film under identical conditions. The solid‐phase photocatalytic degradation mechanism of the nanocomposite films was briefly discussed.     

Photocatalytic decomposition of NO on titanium oxide thin film photocatalysts prepared by an ionized cluster beam technique

Transparent TiO₂ thin film photocatalysts were prepared on transparent porous Vycor glass (PVG) by an ionized cluster beam (ICB) method. The UV‐VIS absorption spectra of these films show specific interference fringes, indicating that uniform and transparent TiO₂ thin films are formed. The results of XRD measurements indicate that these TiO₂ thin films consist of both anatase and rutile structures. UV light (λ > 270 nm) irradiation of these TiO₂ thin films in the presence of NO led to the photocatalytic decomposition of NO into N₂, O₂ and N₂O. The reactivity of these TiO₂ thin films for the photocatalytic decomposition of NO is strongly dependent on the film thickness, i.e., the thinner the TiO₂ thin films, the higher the reactivity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polydimethylsiloxanes-modified TiO2 coatings: The role of structural,morphological and optical characteristics in a self-cleaning surface

The surface modification of TiO₂ thin film with hydrophobic agents has been a good strategy for modulation properties of this versatile material, allowing it to be compatible with a wider range of applications. This is a promising approach in the developing of improved self-cleaning materials; since films prepared with this modification are expected to exhibit photocatalytic and hydrophobic properties. However, these strategies still need to be improved, seeking the design of hydrophobic and photocatalytic structures through faster and simpler procedures, using non-fluorinated polymers. This work proposed the synthesis and characterization of self-cleaning coatings, involving a polydimethylsiloxane (PDMS)/TiO₂ system. TiO₂ thin films were modified with two different types of PDMS: hydroxyl and vinyl-terminated – and prepared by two distinct routes: Route A, which involved a modified TiO₂ sol-gel process, and route B, consisting in the functionalization of TiO₂ films after their calcination. Each route was best suited for a different type of PDMS. The PDMS modification occurred by a covalent linkage, which can allow a better durability of the functionalization on TiO₂ surface. In some cases, the functionalization was heterogeneous and promoted a significant increase in surface roughness, allowing these samples to present hydrophobicity and photocatalytic activity.     

Preparation and photocatalytic properties of macroporous honeycomb alumina ceramics used for water purification

In this work, porous alumina ceramics with highly ordered capillaries were successfully fabricated by ionotropic gelation process of alginate/alumina suspensions. By varying the initial solid loading (10–30 wt%) of slurries, the porosity of alumina ceramics ranged from 60.4% to 79.5% with controlled pore size (180–315 μm). Due to the well-crosslinked macroporous structure and large specific surface areas, the porous ceramics were utilized as the photocatalyst supports of TiO₂ catalysts whose photocatalytic activity was characterized by degrading methyl blue under UV irradiation. TiO₂ coatings prepared by sol–gel method demonstrated excellent adhesion to the substrates. When the solid loading of supports reached 15 wt%, the TiO₂ coatings showed the highest photocatalytic efficiency of 79.52%. Besides, TiO₂ films possessed nearly the same photocatalytic activity as titania/water suspension. Thus, the honeycomb ceramic prepared by self-organization process holds promise for use as photocatalyst supports in water purification without recycling process of powders.     

Visible light photocatalytic activity of TiO2/heat‐treated PVC film

BACKGROUND: Semiconductor TiO₂ has been investigated extensively due to its chemical stability, nontoxicity and inexpensiveness. However, the wide band gap of anatase TiO₂ (about 3.2 eV) only allows it to absorb UV light. TiO₂ nanoparticles modified by conditional conjugated polymers show excellent photocatalytic activity under visible light. However, these conjugated polymers are not only expensive, but also difficult to process. Polyvinyl chloride (PVC) was heat‐treated at high temperature to remove HCl and a C?C conjugated chain structure was obtained. When TiO₂ nanoparticles were dispersed into the conjugated polymer film derived from PVC, this composites film exhibited high visible light photocatalytic activity. RESULTS: The photocatalytic activity of TiO₂/heat‐treated PVC (HTPVC) film was investigated by degrading Rhodamine B (RhB) under visible light irradiation. The photodegradation of RhB follows apparent first‐order kinetics. The rate constants of RhB photodegradation in the presence of the TiO₂/HTPVC films with different mass content of TiO₂ are 16–56 and 4–14 times that obtained in the presence of the pure HTPVC and TiO₂/polymethyl methacrylate (PMMA) composite film, respectively. The TiO₂/HTPVC film showed excellent photocatalytic activity and stability after 10 cycles under visible light irradiation. CONCLUSION: TiO₂/HTPVC film exhibits high visible light photocatalytic activity and stability. Copyright © 2012 Society of Chemical Industry