Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

A mild photochemical approach to the degradation of phenols from olive oil mill wastewater

Photooxidation of cathecol (1) is carried out in aqueous solution at lambda > 300 nm using different sensitizers: rose bengal (RB), 9,10-dicyanoanthracene (DCA), 2,4,6-triphenylpyrylium tetrafluoroborate (Pyryl). The highest degradation is observed in the UV/RB-sensitized reaction (66% after 15 h of irradiation), mineralization and formation of dimers are the final events. This procedure has been extended to tyrosol (2), caffeic acid (3), vanillic acid (4), 4-hydroxycinnamic acid (5) and 4-hydroxybenzoic acid (6) as well as to a mixture of all phenols. A reduced toxicity of the UV/RB-irradiated solutions of cathecol and tyrosol towards alga Ankistrodesmus braunii is also verified.     

Higher intrinsic photocatalytic efficiency of 2,4,6-triphenylpyrylium-based photocatalysts compared to TiO2 P-25 for the degradation of 2,4-dichlorophenol using solar simulated light

The photocatalytic efficiency of two 2,4,6-triphenylpyrylium (TP(+)) based photocatalysts (supported on silica or incorporated inside zeolite Beta, 3wt%) for the degradation of 2,4-dichlorophenol (DCP) in aqueous media has been compared with TiO(2) (Degussa P-25). It was found that the efficiency of the degradation depends on the photocatalytic setup, recirculation through a tubular reactor being highly unfavorable for the TP(+)-based photocatalysts due to the deposition of the silica or zeolite particles. In contrast, high efficiency in DCP disappearance (up to 87%) and in the total organic content decrease (up to 62%) were obtained using a discontinuous batch reactor in which the TP(+) photocatalysts were uniformly suspended. Kinetic studies were also made and DCP degradation follows a first order kinetics. The obtained kinetic constants when corrected to account for the influence of the fraction of light absorbed and the amount of active sites shows that the intrinsic activity of TP(+) adsorbed on silica or incorporated inside zeolite Beta was over one order of magnitude higher than TiO(2) activity.     

Mineralization of dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration process by Fenton oxidation

Fenton's reagent, UV/H2O2 and UV/Fenton's reagent were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) of spent acid in toluene nitration process. The bench-scale experiments were conducted to elucidate the influence of various operating variables on the performance of removal of total organic compounds (TOC) from spent acid, including reaction temperature, concentration of ferrous ion and H2O2 dosage. It is remarkable that organic compounds were completely mineralized by Fenton oxidation, of which removal efficiency is superior to that of UV/H2O2. Nevertheless, it makes slight difference between Fenton oxidation and UV/Fenton oxidation. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of DNT isomers leads to o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene respectively. Besides, the oxidation of 2,4,6-TNT gives the 1,3,5-trinitrobenzene intermediate. Apparently, Fenton oxidation is promising for purification of spent acid industrially.     

A model of natural degradation of 17-α-ethinylestradiol in surface water and identification of degradation products by GC-MS

Over the past decade, the environment has been polluted by a wide spectrum of exogenous chemicals and environmental analysis has become one of the most progressive parts of analytical research. The aim of this work was to determine the kinetics of natural degradation, and to identify the degradation products of the massively used estrogenic drug, 17-α-ethinylestradiol. The photodegradation, oxidation and thermostability conditions were selected according to ICH requirements for pharmaceutical stability testing. A simple 72-h photodegradation study in purified water exhibited significant first-order kinetics with the kinetic constant k = 0.0303 h^?1, and degradation halftime 22.8 h. The basic halftime could be reduced to 17.1 h by the addition of sea salt, and increase in temperature. Monohydroxy, dihydroxy and dehydrogenated derivatives of ethinylestradiol with intact steroidal structure were identified as major degradation products resulting from simple photodegradation. The addition of an oxidative agent significantly accelerated the degradation rate; combined with higher temperature, the degradation halftime was reduced to 1.1 h with the first-order kinetic constant k = 0.632 h^?1. TOC analysis showed a notable decrease of organic mass (18% in 3 days) during oxidation experiments, and confirmed the degradation of steroidal structure.

     

多壁碳纳米管结构对复合光催化剂催化效果的影响

采用溶胶凝胶法制备了多壁碳纳米管负载纳米TiO₂的复合光催化剂（TiO₂/MWCNTs）,以偶氮类染料甲基橙为目标污染物,在自制的光催化反应器上进行了光催化降解反应实验。主要研究同一甲基橙初始浓度（C₀)下,多壁碳纳米管不同管长和管径对复合光催化剂催化效果的影响。结果表明：该降解反应可用一级反应动力学方程描述,反应速率常数k随着多壁碳纳米管管长和管径的增大而增大;与纯纳米TiO₂相比,复合光催化剂对甲基橙的降解率提高了6％～18％,反应速率常数为前者的1.19～2.11倍;采用复合光催化剂的甲基橙光降解溶液自行沉降分离效果较好,静止沉降60 min后达到沉降平衡,剩余浊度为8.5 NTU,下降了90.6％。     

Degradation of X-ray contrast media compounds by combined ozone and ultrasound.

The aqueous degradation of iodinated X-ray contrast media (ICM) by the combination of ozone and ultrasound has been studied. Experiments were conducted at a constant ultrasound frequency of 20 kHz, at five power densities up to 0.235 W/mL, and various ozone centrations. In experiments involving dissolved ozone in solution, the addition of ultrasound significantly decreased the oxidation performance of the dissolved ozone, while the combination of dissolved oxygen and ultrasound gave a greater oxidation performance than ultrasound alone. However, the combination of gaseous ozone and ultrasound was found to give a higher degree of compound degradation than either ozone or ultrasound alone. In the experiments with final effluent, the degradation of ICM compounds by gaseous ozone and ultrasound was found to depend on the ozone dose applied. The degradation of ICM compounds in final effluent was modeled, which was found to moderately overestimate the observed compound degradation.     

Vacuum-ultraviolet (VUV) photolysis of water: Mineralization of atrazine

The versatility and efficiency of the VUV photolysis of water as an “Advanced Oxidation Procedure” for the light-induced oxidative degradation of atrazine as a pollutant of surface and ground waters is evaluated. The oxidation of atrazine using TiO₂ as a photocatalyst has been reported to produce almost stoichiometric amounts of cyanuric acid. Mineralization to CO₂, water and inorganic nitrogen containing ions occurred to a very low extent implying that cyanuric acid is resistant to further degradation under the chosen experimental conditions. Our present results show that in oxygen saturated solutions 50% of the initial atrazine is converted to cyanuric acid, whereas only 10% of the initial atrazine is isolated as cyanuric acid in argon saturated solutions. The results indicate that mineralization is more efficient in not strictly oxidative reaction media.     

Evaluation of UV/TiO(2) and UV/ZnO photocatalytic systems coupled to a biological process for the treatment of bleaching pulp mill effluent

This paper presents an exploratory study of pulp mill bleaching effluent treatment by a biological-photocatalytic coupled system. A fungus, Trametes pubescens, immobilized on polyurethane foam was used to inoculate the biological pre-treatment system. The pretreated effluent was then exposed to a photocatalytic treatment in which two catalysts (TiO₂ and ZnO) and two supports (aluminum foil and Luffa cylindrica) were tested. Catalyst characterization was carried out by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Information about crystalline structure, chemical composition, morphology, homogeneity and distribution on the support surface area was obtained. The overall biological-photocatalytic coupled system achieved degradation of 96% of initial total organic carbon (TOC), 97% of 2-chlorophenol (2-CP), 90% of 2,4-dichlorophenol (2,4-CP) and 99% of 2,4,6-trichlorophenol (2,4,6-TCP). This approach of synergistic coupling of T. pubescens and a semiconductor photocatalyst appears to be a viable alternative for the treatment of these non-biodegradable effluents.     

Keggin型Fe-Mo-Zr杂多酸盐光催化剂的制备及性能研究

利用水热合成法制备了Keggin结构的Fe-Mo-Zr杂多酸盐光催化剂,并利用红外光谱（IR）对催化剂进行了表征。实验以酸性大红（GR）为模拟污染物,考察了在紫外灯照射下,Fe-Mo-Zr杂多酸盐的投加量、污染物的浓度和pH值以及外加H₂O₂对光催化降解效果的影响。实验结果表明,当催化剂的投加量为0.6 g/L,pH为5～7,初始浓度为10 mg/L的GR染料溶液,光照160 min,脱色率可达87.98%。外加H₂O₂可以提高光催化反应效率。     

改性牡蛎壳粉/Ce-N-TiO2吸附-光催化降解草甘膦

通过水热法成功制备了改性牡蛎壳粉/Ce-N-TiO₂复合光催化剂,采用扫描电子显微镜、比表面积测试和X射线光电子能谱分析对其微观形貌、物化性质进行表征分析,并研究其在模拟太阳光下吸附-光催化协同降解草甘膦的降解性能。结果表明：改性牡蛎壳粉单独吸附与Ce-N-TiO₂单独光催化叠加理论降解率低于复合光催化剂协同作用降解率,充分证明两者复合后具有良好的吸附-光催化协同作用;在前120 min内复合材料的降解速率明显高于理论叠加曲线的降解速率,光催化降解草甘膦中有机磷的速率常数由1.179×10⁻² min⁻¹提升至2.441×10⁻² min⁻¹;在实验范围内,改性牡蛎壳粉/Ce-N-TiO₂吸附-光催化协同降解草甘膦的最佳反应条件为：pH为5、实验温度为35 ℃、催化剂投加量为1.0 g·L⁻¹、磁力搅拌器转速为300 r·min⁻¹、光功率设定为400 W。     

Aniline degradation by electrocatalytic oxidation

The degradation of aniline solution in alkaline medium of pH 11.0 by electrocatalytic oxidation has been studied using an electrochemical reactor containing a SnO₂–Sb₂O₃–PtO anode and a Ti cathode, both of 54 cm² area. Hydroxyl radicals (HO^√) are produced at the anode, being tested with the trace catcher salicylic acid and phenol by spectrophotometery and high performance liquid chromatography. Intermediates dianiline, 4-anilino phenol and azobenzol were detected by gas chromatography–mass spectrometry. The existence of HO^√ produced in the aniline degradation was assayed with scavenger tertiary butanol. The results showed that electrocatalytic oxidation is an effective process for the degradation of aniline. A general reaction pathway that accounts for aniline degradation to CO₂ involving those intermediates is proposed.     

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.     

纳米TiO2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩(EP)负载型TiO2,研究其在水中对罗丹明B(RB)的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of phenol over monoclinic BiVO4 under visible light irradiation

BiVO4 powder with monoclinic structure was prepared and used as a visible-light catalyst simultaneously for the photooxidation of phenol and the photoreduction of Cr(VI). The photocatalytic efficiency was found to be rather low for either single phenol solution or single Cr(VI) solution. However, the photocatalytic reduction of Cr(VI) and photocatalytic oxidation of phenol proceed more rapidly for the coexistence system of phenol and Cr(VI) than for the single process, showing synergetic effect between the oxidation and reduction reactions. For the simultaneous photocatalytic reduction-oxidation process, the first-order kinetic constant of phenol degradation was 0.0314 min-1, being about six times higher than that for the photocatalytic process of single phenol. This result reveals the feasibility of using Cr(VI) as the electron scavenger of mBiVO4-mediated photocatalytic process of phenol degradation, and gives us an enlightenment to employ other semiconductor with a better visible light response but with a more positive band edge to efficiently degrade organic pollutants. This is the first report for simultaneous photocatalytic reduction of Cr(VI) and removal of phenol under visible light irradiation using photocatalyst mBiVO4.     

Photocatalytic degradation of the herbicide erioglaucine in the presence of nanosized titanium dioxide: comparison and modeling of reaction kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO2 nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO2 system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir-Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm-1 and 0.984 ppm min-1, respectively. In this work, we also compared the reactivity between the commercial TiO2 Degussa P-25 and a rutile TiO2. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO2 for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO2 process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO2.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.     

Degradation of short-chain alkyl- and alkanolamines by TiO2- and Pt/TiO2-assisted photocatalysis

The photooxidation of C2H5NH2, (C2H5)2NH, HOC2H4NH2, (HOC2H4)2NH and (HOC2H4)3N using TiO2 and Pt/TiO2 as photocatalysts has been investigated. A laboratory set up was designed and a study on the influence of the concentration of the photocatalyst, the pH-value and the structure of the amine performed. The photocatalytic process was optimized with respect to the concentrations of the model substances during degradation. The decrease of the amine concentrations was found to be maximum at a pH of 10. The time-dependence of the formation of cationic breakdown products, such as NH3/NH4 and short-chain alkyl- and alkanolamines was studied by analyses with single column ion chromatography. The experimental data show that the photodegradation follows a Langmuir-Hinshelwood kinetic. The mineralization of the model substances also was monitored by measurements of the decrease of the TOC and of the formation of NO2 and NO3. The different mineralization efficiencies for the model substances studied are discussed with regard to their structure and adsorption behaviour on the photocatalyst. A possible breakdown mechanism involving the electrophilic attack of the hydroxyl radical is given. The applicability of the TiO2-assisted photocatalytic degradation of C2H5NH2 and (C2H5)2NH was tested at the pilot plant-scale with real solar radiation. The degradation rates and products obtained were similar to those found in the laboratory experiments.     

BiVO4联合H2O2或K2S2O8光催化降解布洛芬

以水热法制备了BiVO4光催化剂,并用X射线衍射和扫描电镜对其进行表征。在模拟太阳光照射下,以布洛芬为目标污染物,考察了BiVO4联合H2O2或K2S2O8工艺对布洛芬的光催化降解效果,得出了H2O2或K2S2O8的最佳投加量。通过淬灭实验,研究了光催化联合体系降解布洛芬的机制。X射线衍射谱图表明所合成的BiVO4光催化剂为纯的单斜晶相,扫描电镜结果表明制备的粉末形貌单一,且呈现微球状。加入H2O2或K2S2O8后,一定程度上促进了BiVO4光催化降解布洛芬的效率,H2O2和K2S2O8的最佳投加量分别为3.0 mmol·L-1和1.5 g·L-1。BiVO4/H2O2/hν体系和BiVO4/K2S2O8/hν体系降解水中布洛芬主要是基于·OH自由基的氧化作用。通过对比2个体系中·OH和O2·-对布洛芬降解速率的贡献,发现K2S2O8对BiVO4光催化体系的促进作用远远大于H2O2对该体系的促进作用。     

Decomposition of nitrotoluenes from trinitrotoluene manufacturing process by Electro-Fenton oxidation

Oxidative degradation of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by Electro-Fenton's reagents. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including reaction temperature, dosage of oxygen, sulfuric acid concentration and dosage of ferrous ions. It deserves to note that organic compounds could be completely destructed by Electro-Fenton's reagent with in situ electrogenerated hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra analyzed by gas chromatograph/mass spectrometer, it is proposed that initial denitration of 2,4,6-TNT gives rise to formation of 2,4-DNT and/or 2,6-DNT, which undergo the cleavage of nitro group into o-mononitrotoluene, followed by denitration to toluene and subsequent oxidation of the methyl group. Owing to the removal of both TOC and partial amounts of water simultaneously, the electrolytic method established is potentially applied to regenerate spent acid from toluene nitration processes in practice.