Field solar E. coli inactivation in the absence and presence of TiO2: is UV solar dose an appropriate parameter for standardization of water solar disinfection?

Evaluation of solar treatment in the absence and presence of TiO₂ has been made to assess its effectiveness in reducing bacterial load with respect to drinking water standards.Field experiments under direct solar radiation were carried out using a compound parabolic collector (CPC) placed at the Swiss Federal Institute of Technology (EPFL), Lausanne, Switzerland. Water contaminated with E. coli K12 was exposed to sunlight in different seasons. The obtained results indicate that the presence of TiO₂ accelerates the detrimental action of light. Total photocatalytic disinfection was obtained in both periods of year and no bacterial recovery was observed during 24 h after stopping sunlight exposure. In the absence of TiO₂, total disinfection was not always reached; and bacterial recovery was observed, especially when inactivation was not complete. Bacterial decay was mainly dependent on light intensity. It was also demonstrated that solar UV dose is not a pertinent parameter to standardize solar disinfection. The influence of the following topics on solar water disinfection is also studied in this paper: (a) UV and total solar spectra characteristics (b) volume of phototreated water (c) post-irradiation events.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Electrochemical performance of mesoporous TiO2 anatase

Mesoporous TiO₂ was prepared via a sol–gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant at pH 2. Only the anatase structure was detected after annealing, while the BET specific surface area was measured as being 90 m² g⁻¹ with a rather monomodal pore diameter close to 5 nm. Electrochemical performances were investigated by cyclic voltammetry and galvanostatic techniques. Mesoporous TiO₂ exhibits excellent rate capability (184 mAh g⁻¹ at C/5, 158 mAh g⁻¹ at 2C, 127 mAh g⁻¹ at 6C, and 95 mAh g⁻¹ at 30C) and good cycling stability.     

Single crystalline TiO2 nanorods with enhanced visible light activity for solar hydrogen generation

Single crystalline TiO₂ nanorods and polycrystalline nanotubes were fabricated with same length to investigate the effects of their nanostructures on photocatalytic properties for splitting water. In order to enhance the visible light absorbance, TiO₂ nanorods and nanotubes were sensitized with semiconductor nanoparticles such as CdS, CdSe, and CdS/CdSe, and compared in viewpoint of solar hydrogen generation. It was observed that single-crystalline nanorods showed superior photocatalytic properties to polycrystalline nanotubes, and also the potential level of the nanorods with rutile phase was measured as lower than that of the nanotubes with mixture of anatase and rutile. Further improvement of photo-conversion efficiency was obtained by subsequent heat treatments of the sensitized photoelectrodes. It turns out that the improvement is attributed to the improved crystallinity and the increased size of the nanoparticles during the post-annealing treatments. It was demonstrated that TiO₂ nanorods with lower potential level and a single crystalline phase on FTO glass were advantageous for effective charge injection from the sensitized nanoparticles and transport without recombination lost at grain boundaries.     

g-C3N4/TiO2可见光催化降解磺胺甲恶唑的研究

以TiO₂颗粒和三聚氰胺为原料,采用高温煅烧法制备g-C₃N₄/TiO₂复合光催化材料,研究其对仿生生态系统中磺胺类抗生素的去除效果。利用扫描电子显微镜（SEM）、X射线衍射仪(XRD)、傅里叶变换红外光谱仪（FTIR）、紫外可见分光光度计（UV-vis DRS）对g-C₃N₄/TiO₂进行表征,并研究在可见光条件下g-C₃N₄/TiO₂对溶液中磺胺甲恶唑（SMX）的光催化降解效果。结果表明,g-C₃N₄/TiO₂具有良好的光催化活性,在可见光照射下,当g-C₃N₄/TiO₂投加量为0.2 g·L^-1时,对初始质量浓度为200 μg·L^-1的SMX的去除率可达84.3%。在相同条件下,而g-C₃N₄和TiO₂只能分别去除21.0%和16.0%的SMX,同时在仿生系统中12.37 g·m^-2 g-C₃N₄/TiO₂可以去除95.35%的SMX。通过质谱分析推测,SMX可能的降解路径分别为S—N键断裂、C—N键断裂、S—C键断裂、SMX的羟基化和SMX上氨基的硝化反应,两种可能的中间产物分别为对氨基苯磺酰胺和3-氨基-5-甲基异恶唑。     

Formation of anatase TiO2 by microwave processing

Dye-sensitized solar cells, in which nanoparticles of anatase titanium dioxide play an important role, offer an attractive alternative to conventional photovoltaic cells. The possibility of reducing the required sintering time and temperature for production of these solar cells is investigated. Following synthesis by a sol–gel method, anatase TiO₂ was produced by heat treatment at only 225°C. Using microwave processing, crystallization to the anatase phase was achieved with a shorter heat treatment and a lower temperature than for conventional furnace treatments.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Cobalt doped TiO2: A stable and efficient photocatalyst for continuous hydrogen production from glycerol: Water mixtures under solar light irradiation

Glycerol is the main by-product during the trans-esterification of vegetable oils to biodiesel. In this study, we investigate the process of photocatalytic hydrogen production from glycerol aqueous solution, with the use of cobalt doped TiO₂ photocatalyst under solar light irradiation. Cobalt doped TiO₂ photocatalysts are prepared by impregnation method and these catalysts are characterized by XRD, EDAX, DRS, TEM, EPR and XPS techniques. DRS studies clearly show the expanded photo response of TiO₂ into visible region on impregnation of Co²⁺ ions on surface of TiO₂. XPS studies also show change in the binding energy values of O1s, Ti 2p and Co 2p, indicating that Co²⁺ ions are in interaction with TiO₂. Maximum hydrogen production of 220 μ mol h⁻¹ g⁻¹ is observed on 2 wt% cobalt doped TiO₂ catalysts in pure water under solar irradiation. A significant improvement in hydrogen production is observed in glycerol: water mixtures; and maximum hydrogen production of 11,021 μ mol h⁻¹ g⁻¹ is obtained over 1 wt% cobalt doped TiO₂ in 5% glycerol aqueous solutions. Furthermore, to evaluate some reaction parameters such as cobalt wt% on TiO₂, glycerol concentration, substrate effect (alcohols) and pH of the solution on the hydrogen production activity are systematically investigated. When the catalysts are examined under UV irradiation, a 3–4 fold increase in activity is observed where this activity seems to decrease with time; however, a continuous activity is observed under solar irradiation on these catalysts. The decreased activity could be ascribed the loss of cobalt ions under UV irradiation, as evidenced by EDAX and TEM analysis. A possible explanation for the stable and continuous activity of cobalt doped TiO₂ photocatalysts under solar irradiation is proposed.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.     

Green synthesis of fibrous hierarchical meso-macroporous N doped TiO2 nanophotocatalyst with enhanced photocatalytic H2 production

A new approach to prepare hierarchical and fibrous meso-macroporous N-doped TiO₂ is attempted at room temperature without using templates by the addition of titanium isopropoxide droplets to the ammonia solution. The catalysts are thoroughly characterized by physico-chemical and spectroscopic method to explore the structural, electronic and optical properties. The photocatalytic activities of the catalyst were evaluated with hydrogen generation. NTP catalyst calcined at 400 °C (NTP-400) exhibited 602.7 μmol/3 h H₂ generation from 10 vol.% methanol under visible light. The excellent photocatalytic activity for NTP-400 is attributed to the porous networks existing in our system with uniform N dispersion throughout the catalyst. The hierarchical and fibrous structures allow easy channelization of electron as in the case of nanotubes for effective surface charge transfer. Along with macroporosity, nitrogen incorporation and mesoporosity play some important roles for enhanced photoactivities.     

Photocatalytic degradation of oxytetracycline using TiO2 under natural and simulated solar radiation

The main objective of the present study was to assess the photocatalytic degradation over TiO₂ of an aqueous solution containing 20 mg L⁻¹ of the antibiotic Oxytetracycline (OTC) using simulated solar radiation, seconded by a solar radiation experiment carried out in a pilot plant equipped with Compound Parabolic Collectors (CPCs) under the optimal conditions found in preliminary lab-scale experiments. These comprehended a set of 1 L aqueous experiments with TiO₂ loads ranging from 0.1 to 0.5 g L⁻¹ starting from different initial pH values. These experiments were carried out in a Solarbox equipped with a 1000 W Xe-OP lamp. OTC degradation was followed by HPLC-DAD, while its mineralization was followed by the removal of Total Organic Carbon.Results suggested that 0.5 g L⁻¹ of TiO₂ with no initial pH adjustment (pH ∼ 4.4) was the best combination for the removal of both OTC (100% after 40 min of irradiation; 7.5 kJ L⁻¹ of UV dose) and TOC (>90% after 180 min of irradiation; 38.3 kJ L⁻¹ of UV dose). Under these conditions, the BOD₅/COD ratio rose from almost 0 to nearly 0.5, showing a remarkable improvement in biodegradability, while inhibition percentage of bioluminescence of Vibrio fischeri after 15 min of exposition measured by Microtox® decreased significantly from 35% down to 7%. A scheme of the OTC degradation pathway is proposed, based on the results obtained from this particular experiment.The solar photocatalytic experiment done under the same conditions was carried out in a solar pilot plant equipped with CPCs. OTC and TOC removal was followed as a function of accumulated UV energy entering the reactor. Results showed a 100% OTC and almost 80% TOC removal with 1.8 kJ L⁻¹ and 11.3 kJ L⁻¹ of photo treatment energy, respectively.     

Photocatalytic hydrogen production over CuO and TiO2 nanoparticles mixture

Cheap and efficient photocatalysts were fabricated by simply mixing TiO₂ nanoparticles (NPs) and CuO NPs. The two NPs combined with each other to form TiO₂/CuO mixture in an aqueous solution due to the opposite surface charge. The TiO₂/CuO mixture exhibited photocatalytic hydrogen production rate of up to 8.23 mmol h⁻¹ g⁻¹ under Xe lamp irradiation when the weight ratio of P25 to CuO was optimized to 10. Although the conduction band edge position of CuO NPs is more positive than normal hydrogen electrode, the TiO₂/CuO mixture exhibited good photocatalytic hydrogen production performance because of the inter-particle charge transfer between the two NPs. The detailed mechanism of the photocatalytic hydrogen production is discussed. This mixing method does not require a complicated chemical process and allows mass production of the photocatalysts.     

Spectral response and IV-characterization of dye-sensitized nanocrystalline TiO2 solar cells

Dye-sensitized nanocrystalline TiO₂ solar cells (nc-DSCs) are based on a fundamentally different working principle than solar cells based on semiconductors. This could have implications for the characterization of nc-DSCs. In this study a comparison is made between two methods for determination of the spectral response of nc-DSCs. The standard method for determination of the spectral response according to the ASTM E1021-84 norm appears to be valid for the nc-DSC. The response of the solar cell to pulsed irradiation plays an important role in this determination, since pulsed illumination of the solar cell is involved. The response time of the nc-DSC is related to electron trapping in the TiO₂ and depends on illumination conditions and also on chemical composition of the cell. For this reason, prior to measurements of spectral response of nc-DSCs, the response time of the cell should be measured under the same illumination conditions that are applied during spectral response measurements.     

Development of copper-doped TiO2 photocatalyst for hydrogen production under visible light

The advantage of copper doping onto TiO₂ semiconductor photocatalyst for enhanced hydrogen generation under irradiation at the visible range of the electromagnetic spectrum has been investigated. Two methods of preparation for the copper-doped catalyst were selected – complex precipitation and wet impregnation methods – using copper nitrate trihydrate as the starting material. The dopant loading varied from 2 to 15%. Characterization of the photocatalysts was done by thermogravimetric analysis (TGA), temperature programmed reduction (TPR), diffuse reflectance UV-Vis (DR-UV-Vis), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). Photocatalytic activity towards hydrogen generation from water was investigated using a multiport photocatalytic reactor under visible light illumination with methanol added as a hole scavenger. Three calcination temperatures were selected – 300, 400 and 500 °C. It was found that 10 wt.% Cu/TiO₂ calcined at 300 °C for 30 min yielded the maximum quantity of hydrogen. The reduction of band gap as a result of doping was estimated and the influence of the process parameters on catalytic activity is explained.     

Photocatalytic H2 evolution on a novel CaIn2S4 photocatalyst under visible light irradiation

A novel visible-light-driven photocatalyst CaIn₂S₄ was synthesized using a facile hydrothermal method followed by a post-calcination process. The influence of the calcination temperature and time on the activities of the photocatalyst was investigated. CaIn₂S₄ exhibits optical absorption predominantly in visible region with an optical band gap of 1.76 eV. Considerable activity for hydrogen evolution from pure water was observed without any sacrificial agents or cocatalysts under visible light irradiation. The maximum hydrogen evolution rate achieved was 30.92 μmol g⁻¹ h⁻¹ without obvious deactivation of the photocatalytic activity for four consecutive runs of 32 h.     

Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.     

Optical simulation of transmittance into a nanocrystalline anatase TiO2 film for solar cell applications

Optical simulation has been employed, for the first time, for rigorous evaluation of transmittance into the TiO₂ nanocrystalline film, entering from the fluorine-doped SnO₂ (F-SnO₂) coated glass side, in dye sensitized solar cells. The refractive index of the TiO₂ film with various porosities was determined theoretically, and was in agreement with the data obtained by ellipsometric measurements. The simulation clearly indicates that the transmittance into the TiO₂ film is 85–90% at 450–800 nm, on adjusting the porosity to 0.5–0.75. In contrast, transmittances experimentally determined for the TiO₂ film deposited on F-SnO₂ exhibits 70–83% at 450–800 nm, under-estimating the transmittance by about 10% compared to the simulated results. The simulation method was further substantiated by observing the high IPCE value (85% at 530 nm) for the solar cell using the same TiO₂ film sensitized by ruthenium dye.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

Facile fabrication of Bi2O3/TiO2-xNx nanocomposites for excellent visible light driven photocatalytic hydrogen evolution

Mesoporous Bi₂O₃/TiO_2−xN_x nanocomposites (BiNT) were synthesized by soft chemical template free homogeneous co-precipitation technique. XRD, XPS, TEM, UV-Vis DRS and photoluminescence studies were adapted to determine the structural, electronic and optical properties. The photocatalytic activities of the catalysts were evaluated for water splitting to generate clean hydrogen fuel under visible light irradiation (λ ≥ 400 nm). BiNT-400 catalyst showed highest results towards hydrogen production (198.4 μmol/h) with an apparent quantum efficiency of 4.3%. The pronounced activity of BiNT-400 sample towards hydrogen production was well consistent with high crystallinity, large surface area, proper excitation by N doping and Bi₂O₃ sensitization.