Synthesis of nanocrystalline TiO2 thin films by liquid phase deposition technique and its application for photocatalytic degradation studies

A transparent, high purity titanium dioxide thin film composed of densely packed nanometer sized grains has been successfully deposited on a glass substrate at 30°C from an aqueous solution of TiO₂-HF with the addition of boric acid as a scavenger by liquid phase deposition technique. From X-ray diffraction measurement, the deposited film was found to be amorphous and turns crystalline at 500°C. The deposited film showed excellent adherence to the substrate and was characterized by homogeneous flat surface. TiO₂ thin films can be used as a photocatalyst to clean up organohalides, a class of compound in pesticides that pollute the ground water. Photocatalytic degradation experiments show that indanthrene golden orange dye undergoes degradation efficiently in presence of TiO₂ thin films by exposing its aqueous solution to ultraviolet light. The suitable surface structure and porosity increases the photocatalytic activity. It was also observed that hemin doped TiO₂ thin films break up organohalides at a surprisingly high rate under visible light.     

Photocatalytic degradation of formaldehyde by nanostructured TiO2 composite films

Interest in the photocatalytic oxidation of formaldehyde from contaminated wastewater is growing rapidly. The photocatalytic activity of the nanocrystalline Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film for the degradation of formaldehyde solution under visible light was discussed in this study. The films were characterised by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy, X-ray diffraction (XRD), BET surface area, UV–Vis absorption spectroscopy, and photoluminescence spectroscopy. The FE-SEM results revealed that the Fe³⁺/F^? co-doped TiO₂–SiO₂ film was composed of uniform round-like nanoparticles or aggregates with the size range of 5–10 nm. The XRD results indicated that only the anatase phase was observed in the film. Compared with a pure TiO₂ film and a singly modified TiO₂ film, the Fe³⁺/F^? co-doped TiO₂–SiO₂ composite film showed the best photocatalytic properties due to its strong visible light adsorption and diminished electrons-holes recombination.     

Photocatalytic degradation of aqueous propoxur solution using TiO2 and Hbeta zeolite-supported TiO2

Photocatalytic activity of TiO2 and zeolites supported TiO2 were investigated using propoxur as a model pollutant. Hbeta, HY and H-ZSM-5 zeolites were examined as supports for TiO2. Hbeta was chosen as the TiO2 support based on the adsorption capacity of propoxur on these zeolites (Hbeta>HY=H-ZSM-5). TiO2/Hbeta photocatalysts with different wt.% were prepared and characterized by XRD, FT-IR and BET surface area. The progress of photocatalytic degradation of aqueous propoxur solution using TiO2 (Degussa P-25) and TiO2 supported on Hbeta zeolite was monitored using TOC analyzer, HPLC and UV-vis spectrophotometer. The degradation of propoxur was systematically studied by varying the experimental parameters in order to achieve maximum degradation efficiency. The initial rate of degradation with TiO2/Hbeta was higher than with bare TiO2. TOC results revealed that TiO2 requires 600min for complete mineralization of propoxur whereas TiO2/Hbeta requires only 480min. TiO2/Hbeta showed enhanced photodegradation due to its high adsorption capacity on which the pollutant molecules are pooled closely and hence degraded effectively.     

Preparation of nitrogen co-doped SiO2/TiO2 thin films on ceramic with enhanced photocatalytic activity under visible-light irradiation

In this study, we have successfully deposited N-doped SiO₂/TiO₂ thin films on ceramic tile substrates by sol–gel method for auto cleaning purpose. After dip coating and annealing process the film was transparent, smooth and had a strong adhesion on the ceramic tile surface. The synthesised catalysts were then characterised by using several analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM) and UV-vis absorption spectroscopy (UV-vis). The analytical results revealed that the optical response of the synthesised N-doped SiO₂/TiO₂ thin films was shifted from the ultraviolet to the visible light region. The nitrogen substituted some of the lattice oxygen atoms. The surface area of co-doped catalyst increased, and its photocatalytic efficiency was enhanced. The photocatalytic tests indicated that nitrogen co-doped SiO₂/TiO₂ thin films demonstrated higher than of the SiO₂/TiO₂ activity in decolouring of methylene blue under visible light. The enhanced photocatalytic activity was attributed to an increasing of the surface area and a forming of more hydroxyl groups in the doped catalyst.     

Photocatalytic activity of TiO2 doped with boron and vanadium

Boron (B)- and vanadium (V)-doped TiO(2) photocatalysts were synthesized using modified sol-gel reaction processes and characterized by X-ray diffraction (XRD), Raman spectroscopy and N(2) physisorption (BET). The photocatalytic activities were evaluated by monitoring the degradation of methylene blue (MB). The results showed that the materials possess high surface area. The addition of B favored the transformation of anatase to rutile, while in the presence of V, anatase was the only phase detected. The MB degradation on V-doped TiO(2) was significantly affected by the preparation method. In fact while the presence of V in the bulk did not influence strongly the photoreactivity under visible irradiation, an increase of surface V doping lead to improved photodegradation of MB. The degradation of MB dye indicated that the photocatalytic activities of TiO(2) increased as the boron doping increased, with high conversion efficiency for 9mol% B doping.     

A visible light response TiO2 photocatalyst realized by cationic S-doping and its application for phenol degradation

S-doped TiO2 photocatalyst with high visible light activity was prepared by acid catalyzed hydrolysis method using thiourea (TU) as sulfur source. The catalyst was characterized by DRS, XPS, XRD, FTIR, SEM and N2 adsorption. It was found that cation S6+ was homogeneously incorporated into the bulk phase of TiO2 and substitutes for some of the lattice titanium (Ti4+). Doped S can form a new band above the valence band and narrow the band-gap of the photocatalyst, giving rise to a second absorption edge in the visible light region. The activity of the catalyst was examined by photodegradation of phenol in aqueous solution under both artificial visible light and solar light irradiation. The activity of catalyst was found to be dependent on the doping amount of S and the maximum activity was observed when the catalyst was obtained by calcinated at 600 degrees C with the mass ratio of TU/TiO2=1. Too much of new-generated band-gap structures due to higher S-doping could act as recombination centers for electron-hole pairs. Catalyst with optimum S-doping exhibited the highest activity under both artificial light and solar irradiation for phenol degradation. In addition, doped S also beneficial for the better dispersion, large S(BET) and phase transformation retardation of TiO2.     

Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

Synergy between surface adsorption and photocatalysis during degradation of humic acid on TiO2/activated carbon composites

A photocatalyst comprising nano-sized TiO(2) particles on granular activated carbon (GAC) was prepared by a sol-dipping-gel process. The TiO(2)/GAC composite was characterized by scanning electron microscopy (SEM), X-ray diffractiometry (XRD) and nitrogen sorptometry, and its photocatalytic activity was studied through the degradation of humic acid (HA) in a quartz glass reactor. The factors influencing photocatalysis were investigated and the GAC was found to be an ideal substrate for nano-sized TiO(2) immobilization. A 99.5% removal efficiency for HA from solution was achieved at an initial concentration of 15 mg/L in a period of 3h. It was found that degradation of HA on the TiO(2)/GAC composite was facilitated by the synergistic relationship between surface adsorption characteristics and photocatalytic potential. The fitting of experimental results with the Langmuir-Hinshelwood (L-H) model showed that the reaction rate constant and the adsorption constant values were 0.1124 mg/(L min) and 0.3402 L/mg. The latter is 1.7 times of the calculated value by fitting the adsorption equilibrium data into the Langmuir equation.     

镍、硫共掺杂纳米TiO2的制备及其可见光催化性能

为提高纳米TiO2的可见光催化活性,采用沉淀-浸渍法制备了一种新型Ni和S共掺杂TiO2纳米复合光催化剂.通过紫外-可见(UV-Vis-)漫反射、X-射线衍射(XRD)、透射电子显微镜(TEM)和X-荧光(EDX)等手段对其结晶形态、晶粒尺寸、元素掺杂量和吸光性能等进行了表征.结果显示,催化剂Ni/S/TiO2为锐钛矿晶相,平均粒径约为6～7nm,比表面积高达260.42m2/g,感光范围可拓展到可见光区,且与纯TiO2,S掺杂TiO2和Ni掺杂TiO2相比,光催化剂Ni/S/TiO2的颗粒粒径更小,比表面积更大,光吸收边红移程度更显著.以活性艳蓝198染料溶液为模拟废水,以氙光灯为光源,对光催化剂Ni/S/TiO2的催化活性进行了评价.结果表明,Ni/S/TiO2具有比纯TiO2、S掺杂TiO2和Ni掺杂TiO2更高的可见光催化活性,氙光灯照射120min,活性艳蓝198降解率可达到98.5%.     

石墨烯/TiO2纳米复合材料在光催化领域的研究进展

近年来,石墨烯以其独特的结构和优异的性能成为材料科学领域备受关注的研究前沿和热点。由于石墨烯具有超高的载流子迁移率以及超大的比表面积,将石墨烯与传统的光催化材料复合可显著提高复合材料的光催化性能。综述了石墨烯/TiO2纳米复合材料的研究进展,重点阐述了石墨烯/TiO2纳米复合材料的制备方法及其在光催化领域中的应用,并指出石墨烯/TiO2纳米复合材料的光催化机理是今后研究的重点方向。     

硅藻土/TiO2复合光催化剂制备及表征

以硅藻土和TiCl4为原料,采用水解沉淀法制备了硅藻土/TiO2复合光催化剂。采用XRD、SEM、FTIR和TGA对复合材料进行表征,考察反应温度、硅藻土用量对复合光催化剂结构的影响。结果表明,当反应温度为30℃、硅藻土与TiO2质量比为2∶1时,生成锐钛矿型TiO2,其平均粒径为19.64nm,且大多被吸附进硅藻土的孔隙内;复合光催化剂热稳定性良好,800℃失重率仅为5%。     

Detection of reactive oxygen species (ROS) generated by TiO2(R), TiO2(R/A) and TiO2(A) under ultrasonic and solar light irradiation and application in degradation of organic dyes

In the present work, the rutile, anatase and mixed (rutile and anatase) crystal phase TiO₂ powders were irradiated by ultrasound and solar light, respectively, and the generation of reactive oxygen species (ROS) were detected through the oxidation reaction from 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). The DPCO can be extracted by the mixed solvent of benzene and carbon tetrachloride and the extract liquors display an obvious absorption peak around 563 nm. In addition, the influences of (ultrasonic or solar light) irradiation time, TiO₂ addition amount and DPCI concentration on the quantities of generated ROS were also reviewed. The kinds of generated ROS were determined by using several radical scavengers. At last, the researches on the sonocatalytic and photocatalytic degradation of several organic dyes were also performed. It is wished that this paper might offer some important subjects for broadening the applications of sonocatalytic and photocatalytic technologies.     

Facile synthesis of copper oxide nanotubes decorated by TiO2 nanoparticles,optical and photocatalytic activity in water

Copper oxide nanotubes decorated by TiO₂ nanoparticles (CNTNs) were fabricated by simple three-step method. First, deposition of copper onto cellulose fibres, then thermal oxidation of copper and cellulose fibres and last simply mixing copper oxide nanotubes and TiO₂ nanoparticles (NPs). Scanning electron microscopy, transmission electron microscopy and X-ray diffraction showed that the synthesised nanotubes were monoclinic-structured polycrystalline CuO with diameter and wall thickness of approximately 50～100 nm and 20～25 nm, respectively. Moreover, the diameter of the TiO₂ NPs is about 20～30 nm. Optical properties of the solutions containing copper oxide nanotubes decorated by TiO₂ NPs were studied. Discrete dipole approximation was used for the calculation of absorption, scattering and extinction cross sections of the deposited CNTNs on a glass substrate. Our simulation results show that there are good agreements between the experimental date and the simulation results. Moreover, the photocatalytic tests were done by methyl orange under visible light (λ = 633 nm) irradiation for prepared samples.     

Photocatalytic degradation of three azo dyes using immobilized TiO2 nanoparticles on glass plates activated by UV light irradiation: Influence of dye molecular structure

In order to discuss the effect of chemical structure on photocatalysis efficiency, the photocatalytic degradation of three commercial textile dyes (C.I. Acid Orange 10 (AO10), C.I. Acid Orange 12 (AO12) and C.I. Acid Orange 8 (AO8)) with different structure and different substitute groups has been investigated using supported TiO₂ photocatalyst under UV light irradiation. All the experiments were performed in a circulation photochemical reactor equipped with a 15-W UV lamp emitted around 365 nm. The investigated photocatalyst was industrial Millennium PC-500 (crystallites mean size 5–10 nm) immobilized on glass plates by a heat attachment method. SEM images of the immobilized TiO₂ nanoparticles showed the good coating on the plates, after repeating the deposition procedure three times. Our results indicated that the photocatalytic decolorization kinetics of the dyes were in the order of AO10 > AO12 > AO8. Photocatalytic mineralization of the dyes was monitored by total organic carbon (TOC) decrease, changes in UV–vis spectra and ammonium ion formation. The dye solutions could be completely decolorized and effectively mineralized, with an average overall TOC removal larger than 94% for a photocatalytic reaction time of 6 h. The nitrogen-to-nitrogen double bond of the azo dyes was transformed predominantly into NH₄⁺ ion. The kinetic of photocatalytic decolorization of the dyes was found to follow a first-order rate law. The photocatalysis efficiency was evaluated by figure-of-merit electrical energy per order (E_EO).     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms

Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.     

Photodegradation of methyl orange by photocatalyst of CNTs/P-TiO(2) under UV and visible-light irradiation

A novel nanoscale photocatalyst CNTs/P-TiO(2) was successfully prepared by hydrothermal method. The morphology and the physicochemical properties of the prepared samples were investigated using TEM, XPS, XRD, BET, FTIR, TG-DSC and UV-vis DRS spectroscopy. The photocatalytic activity was evaluated by degradation of methyl orange (MO) dye. The results demonstrated that CNTs/P-TiO(2) nanoparticles could effectively photodegrade MO not only under UV irradiation but also under visible-light (VL) irradiation. The MO degradation performance on CNTs/P-TiO(2) was superior to that of the commercial P25. The optimal mass ratio of CNTs to P-TiO(2) in the nanocomposite catalyst was 5:100. The synergetic effect was discussed in terms of different roles played by phosphorus doping and introducing CNTs into the composite catalysts.     

Degradation of 1,4-dioxane in water using TiO2 based photocatalytic and H2O2/UV processes

1,4-dioxane is a synthetic compound found in industrial effluent and subsequently contaminates water bodies due to its high solubility and high volatility. It is of concern due to its toxic and hazardous nature and has been listed as a class 2B carcinogen. This study involved optimisation of the photocatalytic and H(2)O(2)/UVC processes for 1,4-dioxane removal. Different photocatalysts and loadings were investigated for the degradation of low concentrations of 1,4-dioxane in water including a commercial P25, a synthesised magnetic photocatalyst and an immobilised sol-gel system. A commercial catalyst (Degussa P25) was the most efficient. A lifetime study of the sol-gel reactor showed that the coating was stable over the time period studied. The optimum H(2)O(2) concentration in the H(2)O(2)/UVC process was found to be 30ppm. The addition of H(2)O(2) to the photocatalytic process for 1,4-dioxane removal caused a decrease in rate for the commercial P25 photocatalyst and an increase in rate for the lab-made magnetic photocatalyst.     

Deposition of TiO2 nano-particles on wood surfaces for UV and moisture protection

Deposition of TiO₂ nanoparticles on wood surface was realised to improve the wood stability against ultraviolet (UV) light and moisture degradation. Photocatalytic activity of TiO₂ nanoparticles was utilised for protection of the wood surface. TiO₂ nano-particles were achieved by a sol–gel deposition method using EtOH/TiCl4 solution. Dip-coating process and subsequent annealing were used to realise nano-particles on wood surface. This method of deposition was utilised for the conformal covering of the wood structure as demonstrated by morphological investigation of the prepared samples by field emission scanning electron microscopy. Colour change measurements and Fourier transform infrared spectroscopy were used to analyse the lignin and carbonyl degradation of uncoated and coated wood during the UV exposure. Moisture protection of the coated wood was investigated by measuring the contact angle of the distilled water and wood surface. The measurements showed the UV and moisture protection of the TiO₂ layer.     

Surface Modification of Sericite Using TiO2 Powders Prepared by Alkoxide Hydrolysis: Whiteness and SPF Indices of TiO2-Adsorbed Sericite

Titania (TiO₂) powders have been prepared from the 0.025-M titanium isopropoxide/ethanol solution and the 0.5-M distilled water/ethanol solution. The prepared TiO₂ powders showed an anatase phase and a rutile phase after heat treatment at 500°C for 2 h and 1000°C for 2 h, respectively. The heterocoagulation adsorption between TiO₂ powder and sericite surface in water was achieved in the range of pH 3.63.7 (where this pH range shows a maximum Zeta-potential difference for two powders). On the other hand, an anomalous transformation behavior appeared in the TiO₂-adsorbed sericite after heat treatment at 1000°C. The surface modification of sericite through the TiO₂-adsorption improved the whiteness as well as the SPF (Sun Protection Factor) indices.     

Microstructures and Photocatalytic Properties of S Doped Nanocrystalline TiO2 Films

The nanocrystalline S doped titanium dioxide films were successfully prepared by the improved sol-gel process. Here TiO(C₄H₉O)₄ and CS(NH₂)₂ were used as precursors of titania and sulfur, respectively. The as-prepared specimens were characterized using x-ray diffraction (XRD), x-ray energy dispersive spectroscopy (EDS), high-resolution field emission scanning electron microscopy (FE-SEM), Brunauer-Emmett-Teller (BET) surface area, and ultraviolet-visible diffuse reflectance spectroscopy. The photocatalytic activities of the films were evaluated by degradation of organic dyes in aqueous solution. The results of XRD, FE-SEM, and BET analyses indicated that the TiO₂ films were composed of nanoparticles. S doping could obviously not only suppress the formation of brookite phase but also inhibit the transformation of anatase to rutile at high temperature. Compared with pure TiO₂ film, S doped TiO₂ film exhibited excellent photocatalytic activity. It is believed that the surface microstructure of the modified films is responsible for improving the photocatalytic activity.