Photocatalytic membrane reactor for degradation of acid red B wastewater

Nano-titanium dioxide (TiO₂) photocatalyst was prepared by acid–sol method using tetrabutyl titanate and ethanol, which appeared to be anatase by XRD analysis. The wastewater containing azo dye acid red B was then subjected to photocatalytic degradation with photocatalyst TiO₂ and UV as light source in a slurry photocatalytic membrane reactor, which included a double layer cylindrical photocatalytic reaction zone and a plate frame membrane separation part. Two kinds of ultrafiltration (UF) membranes PVDF700 and PAN700 were applied and the combined process with photocatalysis was operated by a continuous re-circulating mode during treatment. At first, the adsorption characteristic of the titanium dioxide catalyst under different pH values was analyzed and the optimal operation condition of the photocatalytic process was achieved by changing TiO₂ dose and initial concentration of the dye. Then the performance of photocatalyst separation process by ultrafiltration (UF) was investigated. It was found that the degradation of acid red B was followed by first-order kinetics and the efficiency of photocatalysis can be evaluated by the initial reaction rate. Finally, the conglomeration and hydrophilizion phenomena by TiO₂ in the coupling system and its effect to different ultrafiltration membranes were analyzed.     

Photocatalytic and antimicrobial efficacy of PVDF/TiO2 membranes fabricated by solution blow spinning

With its ability to purify water and treat wastewater, photocatalytic membranes have become a promising solution. The membrane's unique properties allow for the separation of solid compounds and the degradation of organic materials through photocatalytic and antibacterial means. Poly(vinylidene fluoride)/titanium oxide (PVDF/TiO₂) composite remain the materials of choice for making these membranes due to their economy, effectiveness, safety, and durability. In this work a photocatalytic membrane reactor (PMR) system was developed using PVDF/TiO₂ membranes fabricated by the solution blow spinning (SBS) process. Obtaining photocatalytic membranes using this method is an efficient and ecological route that overcomes the disadvantage of separating the photocatalyst after the treatment is complete. The results of PMR system showed that the PVDF/TiO₂ membrane could effectively remove total coliforms and E. coli from polluted water. After 10 min of contaminated water circulation through the PMR system, the presence of pathogens was not detected, indicating the efficiency of the obtained membranes.     

Use of porous lavas as supports of photocatalysts

Porous lavas, more precisely pumice stone, are promising supports for TiO₂ used as a photocatalyst. TiO₂ deeply penetrates into pores that favours its retention. Its deposition is convenient and facile and the photocatalytic activity is not significantly affected by the erosion of the surface. The immobilization of TiO₂ on pumice stone gave better results for the photocatalytic degradation of 3-nitrobenzenesulfonic acid than conventional sol–gel dip-coating on cement and red brick. A layer of pumice stone as pellets, fixed on a cement layer and impregnated with TiO₂ is used in a thin film fixed bed reactor, for the photocatalytic treatment of water.     

Sulfanilic acid-modified P25 TiO2 nanoparticles with improved photocatalytic degradation on Congo red under visible light

Visible-light-induced titania/sulfanilic acid nano-composite photocatalysts were prepared and characterized by FTIR, XPS, UV-vis, XRD, and SEM. The results indicate that the formation of Ti-O-S bonds after the modification of P25 TiO₂ nanoparticles with sulfanilic acid ligands extends the photoresponse of the photocatalyst from the UV to the visible range. The photocatalytic activity of the nano-composite photocatalyst was examined by degrading Congo red under visible light, in which its effecting factors such as irradiation time, catalyst dosage, solution pH and the addition of H₂O₂, were investigated in detail. The possible mechanism of photocatalytic degradation under visible irradiation has been also presented.     

Highly visible light responsive metal loaded N/TiO2 nanoparticles for photocatalytic conversion of CO2 into methane

Photocatalytic reduction of carbon dioxide (CO₂) into valuable hydrocarbon such as methane (CH₄) using water as reducing agent is a good strategy for environment and energy applications. In this study, a facile and simple sol-gel method was employed for the synthesis of metal (Cu and Ag) loaded nanosized N/TiO₂ photocatalyst. The prepared photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, BET Surface area analyzer, X-ray photoelectron spectroscopy and UV–vis diffuses reflectance spectroscopy. The photocatalytic conversion of CO₂ into methane was carried out under visible light irradiation (λ≥420 nm) by prepared photocatalysts in order to evaluate the photocatalytic efficiency. The results demonstrate that Ag loaded N/TiO₂ showed enhanced photocatalytic performance for methane production from CO₂ compared to other Cu–N/TiO₂, N/TiO₂ and TiO₂ photocatalysts. The improvement in the photocatalytic activity could be attributed to high specific surface area, extended visible light absorption and suppressed recombination of electron – hole pair due to synergistic effects of silver and nitrogen in the Ag–N/TiO₂ photocatalyst. This study demonstrates that Ag–N/TiO₂ is a promising photocatalytic material for photocatalytic reduction of CO₂ into hydrocarbons under visible light irradiation.     

Synthesis of TiO2 nanoparticles by a combined sol-gel ball milling method and investigation of nanoparticle size effect on their photocatalytic activities

TiO₂ nanoparticles were synthesized by a sol-gel method and the effect of ball milling of dried gel on the particle size has been investigated. The results show that the ball milling has a crucial role in preparation of nanosized TiO₂ powder. Also thermal treatment at different temperatures can control the size of prepared nanoparticles. The photocatalytic activities of TiO₂ nanoparticles with different sizes were studied by photocatalytic degradation of Congo red dye using a homemade photoreactor. The photo degradation of Congo red dye was monitored by UV-Vis absorption measurements. It was found that the nanopowders which were synthesized at 550 °C with average particle size of 55 nm show the maximum photocatalytic activities. These nanopowders which were a mixture of anatase and rutile phases did not show the same photocatalytic effect on Eriochrome black, Bromocresol green, Methyl orange and Rose Bengal dyes.     

Selective adsorption and degradation of rhodamine B with modified titanium dioxide photocatalyst

A new highly selective photocatalyst (RhB‐MIP/TiO₂) was successfully prepared by surface molecular imprinting technique using rhodamine B (RhB) as template molecule. The adsorption kinetics show RhB‐MIP/TiO₂ possessed fast adsorption rate, and adsorption behavior followed the pseudo‐second‐order kinetics. The static binding experiments revealed RhB‐MIP/TiO₂ displayed strong affinity and high adsorption capacity for RhB. Moreover, the equilibrium adsorption rate of RhB‐MIP/TiO₂ for RhB can be well fitted by the Langmuir isotherm model. The thermodynamics parameters indicated that the binding system of RhB‐MIP/TiO₂ was endothermic and spontaneous. Compared with non‐imprinted photocatalyst (NIP/TiO₂), RhB‐MIP/TiO₂ exhibited excellent selectivity toward RhB, whose selectivity coefficient for RhB relative to rhodamine 6G (Rh6G) was 2.99. Selective photocatalytic degradation experiments indicated that the apparent rate constant for the photodegradation of RhB over RhB‐MIP/TiO₂ is 0.0212 min^?1, being 216% of that over NIP/TiO₂ (0.0098 min^?1). Therefore, RhB‐MIP/TiO₂ exhibited higher photocatalytic selectivity toward RhB. The prepared photocatalyst RhB‐MIP/TiO₂ has a promising perspective in industrial wastewater treatment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40890.     

A novel approach for the synthesis of highly active ZnO/TiO2/Ag2O nanocomposite and its photocatalytic applications

The present work is focused on the preparation of hybrid ZnO/TiO₂/Ag₂O nanocomposite for enhanced photocatalytic activity. The resultant samples are characterized by using XRD, SEM, EDX, HR-TEM, UV-DRS, BET and XPS techniques. X-ray diffraction analysis indicates the co-existence of wurtzite, anatase and cubic phases in ZnO/TiO₂/Ag₂O nanocomposite. The band gap energy value of the photocatalyst is 3.39 eV, which has been evidenced from UV–visible diffuse reflectance spectroscopy measurements. Photocatalytic degradation of methylene blue dye has been investigated by using UV–visible spectrophotometer. From the result, it has been concluded that ZnO/TiO₂/Ag₂O nanocomposite has proven to be an efficient photocatalyst under UV irradiation when compared to that of mono and binary oxide systems. Further, the possible photodegradation mechanism is proposed to support the enhancement of photocatalytic activity towards degradation of dyes.     

Increasing of Photocatalytic Performance of TiO2 Nanotubes by Doping AgS and CdS

Highly ordered titanium nanotubes (TiO₂ NTs) photocatalyst was prepared by the anodic oxidation method, and AgS, CdS, and AgS/CdS nanoparticles were doped on the surface of TiO₂ NTs by the successive ion adsorption and reaction (SILAR) method. The photocatalysts were characterized by SEM, EDS, XRD, and potentiostat system. The SEM and EDS analyses respectively show that the average outer diameter of prepared photocatalysts is in the range of 50–120?nm, and the presence of Ti, O, Ag, and Cd is successfully proved. The photocatalytic properties of TiO₂ NTs and doped TiO₂ NTs were studied by measuring the degradation of Methylene Blue (MB) solution. The experimental results show that AgS/CdS/TiO₂ photocatalyst exhibited most efficient photocatalytic activity with 340?µA/cm² photocurrent value. AgS/CdS/TiO₂ NTs photocatalyst shows up to 22.20% higher than TiO₂ NTs, 16.42% higher than CdS/TiO₂ NTs, and 4.3% higher than AgS/TiO₂ NTs.     

Parameter effect on photocatalytic degradation of phenol using TiO2-P25/activated carbon (AC)

P25 powder embedded and TiO₂ immobilized on activated carbon (TiO₂-P25/AC) was prepared by P25 powder modified sol-gel and dip-coated method. The photocatalysts were characterized by XRD, BET, SEM and their photocatalytic activities were evaluated through phenol degradation in a fluidized bed photoreactor. The addition of P25 in the photocatalysts could significantly enhance the photocatalytic activity, and the optimum loading of P25 was 3 g L^?1. The operating parameter results indicated that the optimum pH for phenol degradation was 5.2; the effect of air flow rate gave an optimal value of 2 L min^?1; the increasing of UV light intensity led to an increase of degradation efficiency due to more photons absorbed on the surface of the photocatalyst. The kinetics of the phenol degradation fitted well with the Langmuir-Hinshelwood kinetics model. Finally, the photocatalytic ability of TiO₂-P25/AC was reduced only 10% after five cycles for phenol degradation.     

Developments in photocatalytic antibacterial activity of nano TiO<Subscript>2</Subscript>: A review

TiO₂, which is one of the most explored materials, has emerged as an excellent photocatalyst material for environmental and energy fields, including air and water purification, self-cleaning surfaces, antibacterial and water splitting. This review summarizes recent research developments of TiO₂-based photocatalyst used for photocatalytic antibacterial applications. Several strategies to enhance the efficiency of TiO₂ photocatalyst are discussed, including doping with metal ions, noble metals, non-metals, and coupling with other materials. The mechanism of photocatalytic antibacterial activity in the presence of nano-sized TiO₂ is also discussed. The modified TiO₂ photocatalyst significantly inhibits the growth of bacterial cells in response to visible light illumination. TiO₂ photocatalysis appears to be promising as a route of advanced oxidation process for environmental remediation.     

Enhanced photocatalytic degradation of rutile/anatase TiO2 heterojunction nanoflowers

Rutile/anatase TiO₂ heterojunction nanoflowers were prepared via a facile one-step hydrothermal approach using titanium tetrachloride and urea as the raw materials, cetyl trimethyl ammonium bromide (CTAB) as the template. The prepared TiO₂ nanoflowers were characterized by XRD, SEM, TEM and BET analyses. The photocatalytic performance of the as-prepared TiO₂ samples for methyl blue degradation under simulated solar light was investigated. TiO₂ heterojunction nanoflowers with mixed rutile/anatase phase (prepared with 3 mmol CTAB) give the highest photocatalytic activity. In addition, TiO₂ nanoflowers show excellent stability after 9 cycles under the same conditions. These results suggested that the mixed phase anatase/rutile TiO₂ heterojunction nanoflowers have great potential for the future photodegradation of real dye waste water.     

Preparation of photo-catalytic copolymer grafted asymmetric membranes (N-TiO<Subscript>2</Subscript>-PMAA-g-PVDF/PAN) and their application on the degradation of bentazon in water

Nitrogen-doped titanium dioxide (N–TiO₂) was prepared and supported on a novel copolymer grafted membrane matrix to avoid the problems associated with the removal of spent photocatalyst from treated water. Membranes of poly (methacrylic acid) grafted onto poly (vinylidene difluoride) and blended with poly (acrylonitrile) (PMAA-g-PVDF/PAN) were prepared through a dry–wet phase inversion technique. Methacrylic acid side chains were grafted onto an activated PVDF backbone by the method of reversible addition fragmentation chain transfer polymerization and then the novel photocatalytic asymmetric membranes of N–TiO₂–PMAA-g-PVDF/PAN were prepared. The casting solutions were blended with 1–5 % N–TiO₂ before immersion into the coagulation bath. PVDF and PAN offer several advantages which include: mechanical strength and toughness, chemical resistance, unaffected by long-term exposure to UV radiation, low weight, and thermal stability. N–TiO₂ was prepared through sol-gel synthesis. The photocatalytic membranes were evaluated by degradation process of herbicide bentazon in water. Photodegradation studies revealed that the optimum photocatalyst loading was 3 % N–TiO₂ and the optimum pH was 7 for the degradation of bentazon in water. UV–Vis, TOC and LC–MS analyses confirmed the successful photodegradation of bentazon. A bentazon removal efficiency of 90.1 % was achieved at pH 7. N–TiO₂–PMAA-g-PVDF/PAN membranes were successfully prepared and characterized. These photocatalytic membranes showed great potential as a technology for the effective removal of pesticides from water. According to literature, N–TiO₂–PMAA-g-PVDF/PAN asymmetric photocatalytic membranes have not been prepared before for the purpose of treating agricultural wastewater.     

Photocatalytic degradation of azo dye using TiO2 supported on spherical activated carbon

TiO₂ supported on spherical activated carbon (TiO₂/SAC) was prepared through an ion-exchange method followed by a heat-treatment process. The adsorption characteristic of TiO₂/SAC was evaluated using azo dye methyl orange (MO) as a target substance, and the photocatalytic degradation of MO under UV irradiation was also discussed. A synergistic effect of both the adsorption capacity of activated carbon and the photoactivity of TiO₂ on the removal of MO from aqueous solution was observed. Experimental results revealed that the photocatalytic degradation of MO improved with increasing photocatalyst dosage and followed a pseudo-first order kinetic. After five-cycle runs, TiO₂/SAC still exhibited relatively high photocatalytic characteristic for the degradation of MO. Besides, the prepared TiO₂/SAC can be helpful in the easy separation of photocatalyst from solution after photocatalysis of MO. Furthermore, the use of liquid chromatography/mass spectrometry (LC/MS) technique, identified three intermediates as degradation products during the photocatalytic reaction of MO with TiO₂/SAC.     

Preparation and photocatalysis of TiO2-fluoropolymer electrospun fiber nanocomposites

The preparation and photocatalytic properties of titanium dioxide (TiO₂)-fluoropolymer fiber nanocomposites were studied. The fluoropolymer nanofibers with carboxyl group were prepared by electrospinning. The complex was formed between carboxyl on fluoropolymer electrospun fiber surface and titanium ion, and then the TiO₂ nanoparticles were immobilized on the surface of fluoropolymer electrospun fibers through hydrothermal complex-precipitation. By controlling the reaction conditions, different sizes and numbers of TiO₂ nanocrystals can be obtained. The Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal that an interaction exists between TiO₂ and fluoropolymer fibers. The degradation of methylene blue solution is performed by TiO₂-fluoropolymer fiber nanocomposites under UV irradiation. There may be an adsorption-migration-photodegradation process during the degradation of methylene blue by using TiO₂-fluoropolymer fiber nanocomposites as photocatalyst. The experimental results show that the TiO₂-fluoropolymer fiber nanocomposites have good photocatalytic ability, recycling and stability for the potential applicability in an environmental remediation.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

Microwave photocatalysis III. Transition metal ion‐doped TiO2 thin films on mercury electrodeless discharge lamps: preparation,characterization and their effect on the photocatalytic degradation of mono‐chloroacetic acid and Rhodamine B

BACKGROUND: Mercury electrodeless discharge lamps (Hg‐EDLs) were used to generate UV radiation when exposed to a microwave field. EDLs were coated with doped TiO₂ in the form of thin films containing transition metal ions Mⁿ⁺ (M = Fe, Co, Ni, V, Cr, Mn, Zr, Ag). Photocatalytic degradation of mono‐chloroacetic acid (MCAA) to HCl, CO₂, and H₂O, and decomposition of Rhodamine B on the thin films were investigated in detail. RESULTS: Polycrystalline thin doped TiO₂ films were prepared by dip‐coating of EDL via a sol–gel method using titanium n‐butoxide, acetylacetone, and a transition metal acetylacetonate. The films were characterized by Raman spectroscopy, UV/Vis absorption spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microprobe analysis and by atomic force microscopy (AFM). The photocatalytic activity of doped TiO₂ films was monitored in the decomposition of Rhodamine B in water. Compared with the pure TiO₂ film, the UV/Vis spectra of V, Zr and Ag‐doped TiO₂ showed significant absorption in the visible region, and hence the photocatalytic degradation of MCAA had increased. The best apparent degradation rate constant (0.0125 min^?1), which was higher than that on the pure TiO₂ film by a factor of 1.7, was obtained with the Ag(3%)/TiO₂ photocatalyst. The effect of doping level of vanadium acetylacetonate on the photocatalytic efficiency of the V‐doped TiO₂ was determined. CONCLUSIONS: Transition metal ion‐doped TiO₂ thin films showed significant absorption in the visible region. The metal doped TiO₂ photocatalyst (with an appropriate amount of V, Zr and Ag) on the Hg‐EDLs increased the degradation efficiency of MCAA in a microwave field. Copyright © 2009 Society of Chemical Industry     

Charge transfer properties and photoelectrocatalytic activity of TiO2/MWCNT hybrid

The vertically aligned multiwalled carbon nanotube (MWCNT) arrays on tantalum foils were successfully coated with TiO₂ nanoparticles by a hydrothermal process. The prepared TiO₂/MWCNT hybrid was characterized by scanning electron microscopy and transmission electron microscopy. The charge transfer properties and photocatalytic degradation of rhodamine B with and without bias potential under UV irradiation were investigated. The MWCNTs promoted the separation of photoinduced carriers in the TiO₂, thus enhanced photocatalytic activity. Applying bias potential on the photoanode further enhanced its catalytic activity. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B made this hybrid material promising for photocatalyst and for the development of photoelectrical devices.     

Laser-Induced Silver Nanoparticles on Titanium Oxide for Photocatalytic Degradation of Methylene Blue

Silver nanoparticles doped on titanium oxide (TiO₂) were produced by laser-liquid interaction of silver nitrate (AgNO₃) in isopropanol. Characteristics of Ag/TiO₂ (Ag doped TiO₂) nanoparticles produced by the methods presented in this article were investigated by XRD, TEM, SEM, EDX, and UV-Vis. From the UV-Vis measurements, the absorption of visible light of the Ag/TiO₂ photocatalysts was improved (additional absorption at longer wavelength in visible light region) obviously. The photocatalytic efficiency of Ag/TiO₂ was tested by the degradation of methylene blue (MB) in aqueous solution. A maximum of 82.3% MB degradation is achieved by 2.0 wt% Ag/TiO₂ photocatalyst under 2 h illumination with a halogen lamp.