Influence of TiO2‐Layer Thickness of Spray‐Coated Glass Beads on Their Photocatalytic Performance

TiO₂ is a suitable catalyst for potential photocatalytic processes, e.g., in wastewater treatment. For a technical realization of such processes, the application of immobilized TiO₂ in a continuous process would be desirable. However, since UV radiation has a limited penetration depth into a packed bed of pure TiO₂, supporting it on UV‐transparent glass beads offers the possibility to implement continuous photocatalytic processes in a fixed‐bed reactor. Considering this fact, glass beads were coated with TiO₂ powder in a fluidized‐bed reactor. The coated glass beads with varying TiO₂ layer thickness were tested in the photocatalytic degradation of methylene blue, and the influence of an addition of methyl cellulose during the coating process on the photocatalytic performance was investigated.     

The effect of TiO2 morphology on the surface modification of poly (ethylene terephthalate) for electroless plating

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89?KN?m^?1. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.     

Cellulose reinforced-TiO<Subscript>2</Subscript> photocatalyst coating on acrylic plastic for degradation of reactive dyes

In this study, cellulose reinforced-TiO₂ (C-T) film was coated on acrylic plastic sheet and used for UV photocatalytic degradation of four reactive dyes viz., Reactive Black 5, Reactive Red 11, Reactive Orange 16, and Reactive Red 2 in a falling film reactor (FFR). Slurry comprising cellulose and TiO₂ in suitable weight proportions (5, 10, 15, and 25 wt% cellulose) was prepared and a C-T film was obtained by brush coating on acrylic plastic sheet. The composition yielding adherent film and efficient for the dye degradation was identified. The effect of hydraulic flow rate and solution pH on the stability of the C-T films was also investigated. The photocatalytic coating containing 15 wt% cellulose was found to be adherent and efficient for dye degradation. The photodegradation of the reactive dyes, monitored in terms of decolorization (>80%), and reduction in total organic carbon (TOC) during 5 h followed pseudo first-order kinetics. The mineralization efficiency at 5 h treatment using 15 wt% C-T coating was in the range 75.4–83.3% for all the dyes. On the basis of optical microscopy images, the stability of the C-T films obtained from 15 wt% cellulose was attributed to the interlacing of the cellulose fibers that reinforced the TiO₂ coating.     

Decomposition of formic acid in a photocatalytic reactor with a parallel array of four light sources

The performance of a photocatalytic reactor system with a parallel array of four 6 W blacklight blue fluorescent lamps (wavelength: 300–400 nm) was investigated, based on the decomposition of formic acid in an aqueous solution. An aqueous solution of formic acid (7.8–22.0 gm^?3) was recirculated between the photocatalytic reactor and perfectly‐mixed flow container. The results show that the UV‐light that penetrated through the wall of a glass tube and then passed through the flowing liquid solution accelerated the photocatalytic reaction occurring on the neighboring glass tubes, which greatly contributed to an increase in the reactor activity. This confirms that the arrangement of several light sources in parallel which uses effectively a three‐dimensional space can lead to increased reactor activity and an increase in decomposition rates. A significant reduction in the reaction rate due to a film‐diffusional resistance in the vicinity of the titanium dioxide film was observed. © 2002 Society of Chemical Industry     

Experimental analysis of a photoreactor packed with Pd-BiVO4-Coated glass beads

A photoreactor packed with glass beads coated by palladium nanoparticles-modified BiVO₄ was tested and analyzed in phenol degradation under UV–Visible light. The photocatalytic activity of Pd-BiVO₄ under visible light is higher than TiO₂ under UV light, as we previously reported. In this work, we try to use the Pd-BiVO₄ in a large scale by coating the glass beads with it, a potentially industrial-scale use. For comparison, a flat-plate reactor and a slurry reactor were also examined. The photocatalytic activity of Pd-BiVO₄ in phenol degradation was found to be higher than that of TiO₂ in all systems (slurry, flat-plate, and packed beads reactor [PBR]). Furthermore, PBR exhibited higher energy efficiency compared to the flat-plate reactor in phenol oxidation. The superior performance of this reactor is due primarily to the highly exposed catalyst surface area, high mass transfer coefficient, and effective delivery of both photons and reactants to the catalyst surfaces. © 2018 American Institute of Chemical Engineers AIChE J, 65: 132–139, 2019     

Effects of V and Zn codoping on the microstructures and photocatalytic activities of nanocrystalline TiO2 films

To enhance the photocatalytic activity of TiO₂, V and Zn co-doped TiO₂ films were synthesized by the sol–gel method. The experimental results indicated that the films were composed of round-like nano-particles or aggregates. V and Zn codoping could not only obviously increase the specific surface area of TiO₂ but also result in the narrowed band gap of TiO₂ sample. The photocatalytic activities of the TiO₂ films were evaluated by the photocatalytic decomposition of organic dyes in aqueous solution. Compared with un-doped TiO₂ film or single doped TiO₂ film, V and Zn co-doped TiO₂ film exhibited excellent photocatalytic activities under both UV light and visible light. The improvement mechanism by V and Zn codoping was also discussed.     

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.     

Preparation and photocatalytic performance of nano-TiO2-coated beads for methylene blue decomposition

Fluidized bed chemical vapor deposition (FB-CVD) method using tetra iso-propoxide as a precursor of TiO₂ was applied to achieve TiO₂ coating onto various types of beads. The substrates of the beads included alumina, silica-gel, and glass, and these beads were of small diameter (ca. 1–2 mm). From our investigation of TiO₂-coated surfaces of these beads, we observed formation of TiO₂ coating down to ～35 nm in thickness. In addition, we found that both the type of the substrate and condition of coating process had effect on the surface morphology of coated beads. From combined studies of the surface morphology and the photocatalytic decomposition of methylene blue, we detected characteristic features of coated surface which were associated with high photocatalytic performance. Provided are the explanations to account for the high photocatalytic performance found for TiO₂-coated beads of silica-gel substrate.     

Solar photocatalytic decolorization of synthetic dye solution using pilot scale slurry type falling film reactor

Ag deposited TiO₂ was prepared by simple chemical reduction method and its photocatalytic efficiency was evaluated for the decolorization of methylene blue dye using pilot scale slurry type falling film reactors (FFR) under sunlight. The characterization of the prepared catalysts by XRD, TEM, EDAX, DRS and PL confirmed that silver, which acts as electron trap, was deposited over the TiO₂ surface. The operational parameters, such as catalyst loading, concentration of the dye solution, pH of the slurry, addition of oxidizing agents and effect of different substrates, were optimized. The photocatalytic efficiency of Ag deposited TiO₂ increased two-fold times than pure TiO₂ and the maximum decolorization of dye was observed under acidic conditions. The reaction rate significantly increased with the addition of oxidizing agent H₂O₂. The ceramic tile as well as double skin reactor have higher photocatalytic efficiency than glass as substrate. In addition, Ag-deposited TiO₂ photocatalyst could be easily recovered by simple sedimentation process and reused for repeated experimental cycles with more than 95% decolorization efficiency.     

A Novel Method for Preparing V-doped Titanium Dioxide Thin Film Photocatalysts with High Photocatalytic Activity Under Visible Light Irradiation

The liquid phase deposition (LPD) method was successfully used for preparing V-doped TiO₂ thin film photocatalysts. In this simple and easily-controlled process, V-doped anatase TiO₂ thin films were directly deposited on a soda lime glass substrate placed in an aqueous solution containing Ti- and V-fluoro complex ions, followed by annealing. The thin films were analyzed by XRD, XPS, UV-vis. V⁴⁺ ions were introduced into the lattice of TiO₂ through in-situ substituting Ti⁴⁺. The absorption edge of V-doped TiO₂ films shifted to visible light region. The highly efficient photocatalytic activity was verified by the decomposition of methylene blue under visible light irradiation.     

Facile preparation of Na-free anatase TiO2 film with highly photocatalytic activity on soda-lime glass

Na-free anatase TiO₂ film was prepared on soda-lime glass (SL-glass) from a TiF₄ aqueous solution upon addition of boric acid at 60 °C. It was found that the as-prepared TiO₂ film before calcination showed a higher photocatalytic activity than the calcined sample (500 °C). This could be attributed to the fact that the calcined TiO₂ film contained decent Na⁺ ions, which was diffused from the SL-glass substrate into the TiO₂ film during calcination, resulting in the decrease of photocatalytic activity.     

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.     

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.     

Preventing Sodium Poisoning of Photocatalytic TiO2 Films on Glass by Metal Doping

Titanium dioxide (TiO₂) has received much attention as a photocatalyst, specifically in applications that require a mechanically robust thin film. TiO₂ is particularly useful because it does not absorb visible light, making it well suited for coatings on glass. Photocatalytic activity of TiO₂ films is strongly dependent on the substrate and it has been well established that sodium diffusion from glass has a negative effect on this activity. While the prevention of sodium poisoning is possible through the use of a precoating, this requires an additional coating and/or calcination step. Other remedies, such as acid treatment of the glass surface, are also time consuming. Therefore, it is a more attractive option to negate the effects of sodium diffusion without a separate processing step. In this paper, we examined the effects of silver, cobalt, copper, gallium, molybdenum, and tantalum doping on the prevention of sodium poisoning of sol–gel TiO₂ films by comparing the photocatalytic activities on glass and SiO₂ precoated glass. While sodium poisoning degraded the photocatalytic activity of undoped TiO₂ films by 70%, it was only 10% for Mo- and Ta-doped TiO₂ films. Molybdenum was superior to other dopants in terms of photocatalytic activity, both in the presence of sodium and in a sodium-free environment.     

Development of an optical fiber monolith reactor for photocatalytic wastewater Treatment

A photocatalytic reactor, which employs a ceramic multi-channel monolith as a support for TiO₂ and bare quartz fibers inserted inside the monolithic channels as both a light-transmitting conductor and a support for TiO₂, was constructed and tested for water treatment by investigating the photocatalytic degradation of o-dichlorobenzene (DCB) and phenanthrene (PHE). This configuration provides a higher surface area for catalyst coating per unit reactor volume compared to the continuous annular reactor (CAR) and optical fiber reactor (OFR). The light distribution profile inside each cell of the monolith is analyzed. Exponential decay of light was observed in propagation along the quartz fiber core and penetration into the TiO₂ film. Optimum thickness of TiO₂ layer on the optical fiber was found to be ≈ 0.4 μm in this study. The kinetics of DCB and PHE degradation were pseudo-first order. The effect of the water flow velocity was investigated and showed that the operation was in the mass transfer control regime. Overall rate constants were extracted from the experimental data; and these were then used to calculate the apparent quantum efficiency of photocatalytic degradation. Greater apparent quantum efficiency was observed for the optical fiber monolithic reactor (OFMR) compared with that of the CAR.     

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.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

Approach to a pulse photoelectrocatalytic process for the degradation of organic pollutants

Ag–TiO₂ composite film was supported on indium–tin oxide glass (ITO) by a dip‐coating and subsequent photodeposition procedure. The composite film was employed as the photoanode for photoelectrocatalytic (PEC) degradation of Acid Orange II. The degradation efficiency for the PEC process on the Ag–TiO₂/ITO electrode with a 0.8 V anodic bias is significantly higher than that for a photocatalytic process on Ag–TiO₂/ITO film or for a PEC process on a neat TiO₂/ITO photoanode. A new PEC technology with a pulse anodic bias was also proposed in order to solve the problem of the loss of deposited Ag from the Ag–TiO₂/ITO. It was found that the PEC process with a 4.2 V pulse anodic bias could much more efficiently degrade Acid Orange II than that with a constant anodic bias of 0.8 V or 4.2 V. Moreover, when the duration of the open and close circuit time was identical, the treatment efficiency was observed to be optimal. Copyright © 2003 Society of Chemical Industry     

Synthesis of TiO<Subscript>2</Subscript> Nanoparticles by Microemulsion/Heat Treated Method and Photodegradation of Methylene Blue

In this work, TiO₂ nanoparticles were prepared by microemulsion (ME)/heat treated method and its photodecomposition property of methylene blue. Microemulsion (ME) consisted of water, cyclohexane and an anionic surfactant such as bis (2-ethylhexyl) sodium sulfosuccinate (AOT). Titanium tetraisopropoxide (TTIP) was dropped into the ME solution and then then TiO₂ nanoparticles were formed by the hydrolysis reaction between TTIP in the organic solvent and the water in the core of ME. The smallest diameter of the particles was 20 nm in the system of cyclohexane with surfactant when the molar ratio of water to surfactant was 2. The effect of the process parameters (water/surfactant ratio, different temperatures) on the final characteristics has been investigated, in terms of structural phase and particle size. The TiO₂ nanoparticles were characterized by means of X-ray diffraction, Transmission and scanning electron microscopy, Fourier-Transformed infrared and differential thermal analysis. TiO₂ nanoparticles prepared in this condition were collected as amorphous powder, and converted to anatase phase at less than 350 °C, which is lower than the ordinal phase transition temperature. The crystallite size and crystallinity increase with an increase of heat treated s temperature. The particles are shown to have a spherical shape and have a uniform size distribution. The size of nanoparticles raises with an increase of water/surfactant ratio. In the photocatalytic decomposition of methylene blue, the photocatalytic activity is mainly determined by the crystallinity of TiO₂. In addition, the TiO₂ heat treated at 350 °C shows the highest activity on the photocatalytic decomposition of methylene blue (k = 1.7 × 10⁻² min⁻¹).     

A novel hierarchical Pt- and FTO-free counter electrode for dye-sensitized solar cell

A novel hierarchical Pt- and FTO-free counter electrode (CE) for the dye-sensitized solar cell (DSSC) was prepared by spin coating the mixture of TiO₂ nanoparticles and poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) solution onto the glass substrate. Compared with traditional Pt/FTO CE, the cost of the new CE is dramatically reduced by the application of bilayer TiO₂-PEDOT:PSS/PEDOT:PSS film and the glass substrate. The sheet resistance of this composite film is 35 Ω sq⁻¹ and is low enough to be used as an electrode. The surface morphologies of TiO₂-PEDOT:PSS layer and modified PEDOT:PSS layer were characterized by scanning electron microscope, which shows that the former had larger surface areas than the latter. Electrochemical impedance spectra and Tafel polarization curves prove that the catalytic activity of TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE is higher than that of PEDOT:PSS/FTO CE and is similar to Pt/FTO CE''s. This new fabricated device with TiO₂-PEDOT:PSS/PEDOT:PSS/glass CE achieves a high power conversion efficiency (PCE) of 4.67%, reaching 91.39% of DSSC with Pt/FTO CE (5.11%).