Capability of novel ZnFe₂O₄ nanotube arrays for visible-light induced degradation of 4-chlorophenol

Highly ordered ZnFe₂O₄ nanotube arrays were successfully prepared by anodic aluminum oxide templates from sol-gel solution. The results from environmental scanning electron microscopy and X-ray photoemission spectroscopy indicated that the as-prepared samples were vertically aligned spinel ZnFe₂O₄ nanotube arrays, and the nanotubes were uniform along the axial direction with an average diameter of approximately 200 nm. The absorption edge of ZnFe₂O₄ nanotube arrays shifted to a higher energy in the UV-Vis absorption spectrum compared with that of ZnFe₂O₄ nanoparticles film. The synthesized ZnFe₂O₄ nanotube arrays exhibited excellent photocatalytic capability for degradation of 4-chlorophenol under visible-light irradiation. The main intermediate degradation species of 4-chlorophenol identified by liquid chromatography-mass technique were benzoquinone, hydroquinone, hydroxybenzoquinone and 2-peroxy-o-dihydroxybenzene. The degradation pathways of 4-chlorophenol under visible-light irradiation was derived and discussed by interpreting the observations of the intermediate species in the photocatalytic reactions.     

Photocatalytic degradation of an azo dye using N-doped NaTaO3 synthesized by one-step hydrothermal process

N-doped NaTaO₃ compounds (NaTaO_3−xN_x) with nano-cubic morphology were successfully synthesized by one-step hydrothermal method and Methyl Orange (MO) was used as a model dye to evaluate their photocatalytic efficiency under visible-light irradiation. The as-prepared NaTaO_3−xN_x samples were characterized by various techniques, such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and UV-vis diffuse reflectance spectra and GC-MS. The results indicate that NaTaO_3−xN_x displays a pure perovskite structure when the synthesis temperature is higher than 180 °C. Moreover, as observed by SEM images, the particles of resultant NaTaO_3−xN_x show cubic morphology with the edge length of 200-500 nm, which can be easily removed by filtration after photocatalytic reaction. Doping of N increases the photocatalytic activity of NaTaO₃, and NaTaO_2.953N_0.047 shows the highest visible-light photocatalytic activity for the degradation of MO. Based on the experiment results, a possible mechanism of the photocatalysis over NaTaO_3−xN_x and the photodegradation pathway of MO were proposed.     

Significance of analytical parameters for the understanding of natural organic matter in relation to photocatalytic oxidation

In this review, special interest was devoted to provide information on the surrogate parameters expressing both quality and quantity of organic matter for the understanding of the photocatalytic oxidation of humic substances. Detailed investigation was directed to the application of photocatalysis with reference to source, origin and modeling of organic matter. Evaluation of the literature findings emphasizes that organic matter taken from natural waters are site specific and should be characterized in detail to be comparable to other studies. Taking into account the photocatalytic degradation studies of natural organic matter, humic substances, humic acids and fulvic acids in slurry systems, a procedure could be deduced that depends on the selection of a standard model sample with a representative concentration, selection of a standard photocatalyst and dose (e.g., TiO₂ Degussa P-25, 0.25 mg mL⁻¹), application of standardized reaction conditions such as light intensity, pH, and temperature. Furthermore, standardized filtration step avoiding organic leaching and selection of the most suitable analytical parameter are the crucial points to be considered. The use of such a protocol could form a basis for the determination of “relative degradation efficiency” of any sample containing natural organic matter, humic substances, humic acids and fulvic acids regardless of dependency on source and origin.     

太阳光下降解久效磷的催化剂研究

以ＴｉＯ_２为基体,用掺杂某些金属或离子的方法,提高ＴｉＯ_２;在太阳光下的催化活性。从多种掺杂催化剂中,筛选出太阳光下降解人效磷的有效催化剂 Ｆｅ~３＋／ＴｉＯ_２,经 ３ ｈ阳光照射,久效磷的矿化率达 ９０％。 Ｆｅ~（３＋）在待降解液中的最适宜浓度为 ２．０×１０~（－４）ｍｏｌ／Ｌ。     

Cr3+离子掺杂对负载TiO2薄膜光催化活性的影响

以钛酸丁酯和CrCl3·6H2O为原料,采用溶胶-凝胶法在钛片、玻璃、釉面瓷砖、陶瓷、不锈钢和铝片六种载体上制备了Cr3 掺杂TiO2薄膜。讨论了不同Cr3 掺杂浓度下,不同载体表面上制备的TiO2薄膜对甲基橙脱色率的影响。试验结果表明:Cr3 对TiO2薄膜的掺杂效果与载体的类型密切相关,并且不同载体其Cr3 掺杂的最佳浓度也不同。Cr3 掺杂后,TiO2薄膜光催化活性提高最大的是釉面瓷砖,其次是玻璃、钛片、铝片、陶瓷,最差的是负载不锈钢。     

Comparison of Numerical and Experimental Results for the Evaluation of the Depollution Effectiveness of Photocatalytic Coverings in Street Canyons

Towards the aim of improving the air quality in the urban environment via the application of innovative TiO₂ based photocatalytic coverings, a field campaign took place within the frame of the EU PICADA project () to asses the expected depollution efficiency of such materials under realistic conditions. Furthermore, extensive numerical modeling was performed via the application of the RANS CFD code for microscale applications MIMO, in an effort to asses the sensitivity of the developing flow field and the corresponding dispersion mechanism and hence of the depollution efficiency of the PICADA products on a wide range of factors, with most notably the length of the street canyon, the thermal exchange between the heated street canyon walls and the air and the approaching wind direction. For the needs of the PICADA project a new, simple module had to be implemented into MIMO to be able to model the removal of NO_x from a street canyon whose walls have been treated with a photocatalytic product. The model simulations results presented in this paper, show that MIMO is indeed capable of predicting the effectiveness of the photocatalytic products in question. At the same time, they reveal a strong dependence of the developing flow and concentration fields inside the field site street canyon configuration on most of the aforementioned factors with most notably the direction of the approaching wind.

二氧化钛复合纸板对壬基酚聚氧乙烯醚水溶液的光催化降解

制备了一系列无机物含量大于80%的植物纤维/吸附剂/二氧化钛复合纸板,考察了复合纸板对壬基酚聚氧乙稀醚(NP-10)水溶液的光催化降解性能.结果表明,二氧化钛复合纸板对NP-10具有优良光催化降解性能,紫外光照34h后浓度为50mg·mL-1的NP-10的降解率达80%以上,光照前后NP-10水溶液的化学需氧量(COD)的变化表明,光催化降解可导致NP-10矿化.活性炭对二氧化钛光催化降解有协同作用,其在无机粉体中的质量分数为15%时,复合纸板的光催化降解性能最好.过氧化氢可大幅提高复合纸板的光催化降解性能,其最佳浓度为20mg·mL-1.二氧化钛复合纸板在NP-10水溶液中的稳定性好,重复使用10次后其质量损失小于2%,光催化降解性能不变.     

光催化氧化苯酚中间产物的分析与降解途径探讨

采用光催化氧化法降解苯酚溶液,利用液相色谱对苯酚及其中间产物进行了定性、定量分析。考察了投加H2O2对中间产物浓度变化的影响。根据中间产物的产生情况及浓度变化,推测了苯酚光催化降解的反应途径。     

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m~2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD(X-ray diffraction), SEM(scanning electron microscopy), TEM(transmission electron microscopy), FT-IR(Fourier transform infrared spectroscopy), TGA(thermogravimetric analysis), DSC(differential scanning calorimetry) and BET(Brunauer–Emmett–Teller) surface area. The degradation of dichlorophenol-indophenol(DCPIP) under ultraviolet(UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.