Study of the degradation behaviour of dimethoate under microwave irradiation

In this work, the degradation of dimethoate under microwave irradiation assisted advanced oxidation processes (MW/oxidants) were studied. The efficiencies of the degradation of dimethoate in dilute aqueous solutions for a variety of oxidants with or without MW irradiation were compared. The results showed that the synergistic effects between MW and K(2)S(2)O(8) had high degradation efficiency for dimethoate. Simultaneously, UV/TiO(2)/K(2)S(2)O(8) photocatalytic oxidation degradation of dimethoate was investigated. The experimental results indicated that the method of microwave degradation of organic pollutants in the presence of oxidant could reduce reaction time and improve product yield. Microwave irradiation was an advisable choice for treating organic wastewaters and has a widely application perspective for non- or low-transparent and fuscous dye wastewaters.     

Microwave assisted rapid and complete degradation of atrazine using TiO(2) nanotube photocatalyst suspensions

A technology, microwave-assisted photocatalysis on TiO(2) nanotubes, which can be applied to degrade atrazine rapidly and completely, was investigated. TiO(2) nanotubes were prepared, and confirmed by XRD, TEM and ESR. Microwave-assisted photocatalytic degradation of atrazine in aqueous solution was investigated. The result indicates that atrazine is completely degraded in 5min and the mineralization efficiency is 98.5% in 20min, which is obviously more efficient than that by the traditional photocatalytic degradation methods. It may be attributed to the intense UV radiation generated by electrodeless discharge lamps under microwave irradiation, the increased number of OH, additional defect sites on TiO(2) under the irradiation of microwave and larger specific surface area of TiO(2) nanotubes which could adsorb more organic substances to degrade than TiO(2) nanoparticles. Along with the degradation of atrazine, the concentrations of Cl(-) and NO(3)(-) increase gradually. In 20min [Cl(-)] and [NO(3)(-)] are 3, 27.8mg/L, respectively, which are close to their stoichiometric values. The major intermediates of atrazine were identified by HPLC/MS and possible degradation pathways of atrazine in microwave-assisted photocatalysis on TiO(2) nanotubes were proposed.     

Photocatalytic ozonation of dimethyl phthalate with TiO2 prepared by a hydrothermal method

TiO(2) was prepared by a hydrothermal method at a low temperature and used to degrade and mineralize dimethyl phthalate (DMP). TiO(2) was characterized by XRD, TEM, BET and UV-vis techniques. The characteristics of TiO(2) prepared by a hydrothermal method (h-t TiO(2)) included a good crystalline anatase phase, greater surface area, stronger absorption to UV light wavelength and lower agglomeration than TiO(2) prepared by a classic sol-gel method (s-g TiO(2)). The photocatalytic activity of h-t TiO(2) prepared under optimal hydrothermal condition (180°C for 10h) was 2.5 times higher than that of s-g TiO(2) in degrading DMP. The process of photocatalysis combined with UV irradiation and ozonation (TiO(2)/UV/O(3)) considerably improved the mineralization and degradation of DMP compared to photocatalysis combined with UV irradiation (TiO(2)/UV), ozonation combined with UV irradiation (UV/O(3)), and ozonation alone (O(3)). A kinetic study showed the mineralization in TiO(2)/UV/O(3) followed the Langmuir-Hinshelwood model.     

Photocatalytic degradation of methylene blue in TiO2 aqueous suspensions using microwave powered electrodeless discharge lamps

Photocatalytic degradation of methylene blue (MB) in TiO(2) aqueous suspensions using microwave (MW) powered electrodeless discharge lamps (EDLs) was studied. MB of initial concentration 100 mg/l was mainly decomposed in the process of photocatalytic degradation using EDLs (PCD/EDLs) after 15 min of irradiation. The corresponding mineralization efficiency was 45%. The influence of factors as EDLs, solution volume and TiO(2) catalyst dosage on the decomposition of MB in the PCD/EDLs process was also investigated. The optimal decomposition efficiency was observed when EDLs-4 (four 10 mm x 50 mm EDLs), solution volume of 50 ml and TiO(2) catalyst dosage of 1-4 g/l were used in the study. The PCD/EDLs process was promising in treating MB polluted water.     

La/TiO2-SiO2薄膜的光催化性能研究

采用溶胶-凝胶法制备了不同掺杂量的La／TiO2-SiO2复合薄膜．通过XRD、FE-SEM和AFM研究了复合薄膜的微观结构，采用紫外光照射下亚甲基蓝的分解实验比较薄膜的光催化性能．结果表明：La掺杂可显著提高TiO2-SiO2复合薄膜的光催化活性，以5％掺杂量为最佳，其光降解率比掺杂前提高了约23％．薄膜活性提高的主要原因是La掺杂后细化了TiO2的晶粒，提高了薄膜的比表面积，使其具有更高的氧化还原电势，La^3＋取代Ti^4＋进入到TiO2晶格，引起晶格膨胀，这种不同价离子的取代导致TiO2粒子表面电荷分布不平衡，从而提高了光生电子-空穴的分离效率．     

微波掺氮有序多孔TiO2材料的制备与性能

采用晶胶模板法制备了有序多孔TiO<,2>材料,在微波辐照条件下对其掺氮改性,利用扫描电镜(SEM)、X射线衍射(XRD)、光电子能谱(XPS)方法对掺氮TiO<,2>材料进行表征,并研究掺氮前后TiO<,2>材料光催化性能.实验结果显示,通过晶胶模板法所制备的有序多孔TiO<,2>材料的整体比较致密,但局部有孔洞的塌...     

Different methods in TiO2 photodegradation mechanism studies: gaseous and TiO2-adsorbed phases

The development of photocatalysis processes offers a significant number of perspectives especially in gaseous phase depollution. It is proved that the photo-oxidizing properties of photocatalyst (TiO(2)) activated by UV plays an important role in the degradation of volatile organic compounds (VOC). Heterogeneous photocatalysis is based on the absorption of UV radiations by TiO(2). This phenomenon leads to the degradation and the oxidation of the compounds, according to a mechanism that associates the pollutant's adsorption on the photocatalyst and radical degradation reactions. The main objective of the study is the understanding of the TiO(2)-photocatalysis phenomenon including gaseous and adsorbed phase mechanisms. Results obtained with three different apparatus are compared; gaseous phases are analysed and mechanisms at the gaseous phase/photocatalyst interface are identified. This study leads to improve understanding of various mechanisms during pollutant photodegradation: adsorption of pollutants on TiO(2) first takes place, then desorption and/or photodegradation, and finally, desorption of degradation products on TiO(2). The association of analytical methods and different processes makes the determination of all parameters that affect the photocatalytic process possible. Mastering these parameters is fundamental for the design and construction of industrial size reactors that aim to purify the atmosphere.     

Solar photocatalytic degradation of some hazardous water-soluble pesticides at pilot-plant scale

The technical feasibility and performance of photocatalytic degradation of six water-soluble pesticides (cymoxanil, methomyl, oxamyl, dimethoate, pyrimethanil and telone) have been studied at pilot-plant scale in two well-defined systems which are of special interest because natural solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. TiO(2) photocatalysis tests were performed in a 35L solar pilot plant with three Compound Parabolic Collectors (CPCs) under natural illumination and a 75L solar pilot plant with four CPC units was used for homogeneous photocatalysis tests. The initial pesticide concentration studied was 50 mg L(-1) and the catalyst concentrations employed were 200 mg L(-1) of TiO(2) and 20 mg L(-1) of iron. Both toxicity (Vibrio fischeri, Biofix) and biodegradability (Zahn-Wellens test) of the initial pesticide solutions were also measured. Total disappearance of the parent compounds and nearly complete mineralization were attained with all pesticides tested. Treatment time, hydrogen peroxide consumption and release of heteroatoms are discussed.     

Study on photocatalytic degradation of several volatile organic compounds

The gas-phase photolytic and photocatalytic reactions of several aromatics and chlorohydrocarbons were investigated. The experimental results revealed that chlorohydrocarbons like trichloroethylene, dichloromethane and chloroform could be degraded through either photolysis or photocatalysis under irradiation of germicidal lamp, and the elimination rate of chlorohydrocarbons through photolysis was quicker than that through photocatalysis. UV light from a germicidal lamp could directly lead to degradation of toluene but could hardly act on benzene. The photodegradation rate for these volatile organic compounds (VOCs) through photolysis followed an order: trichloroethylene>chloroform>dichloromethane>toluene>benzene>carbon tetrachloride, and through photocatalysis followed: trichloroethylene>chloroform>toluene>dichloromethane>benzene>carbon tetrachloride. Besides, a series of modified TiO2 photocatalysts were prepared by depositing noble metal, doping with transition metal ion, recombining with metal oxides and modifying with super strong acid. Activity of these catalysts was examined upon photocatalytic degradation of benzene as a typical compound that was hard to be degraded. It indicated that these modification methods could promote the activity of TiO2 catalyst to different extent. The apparent zero-order reaction rate constant for degrading benzene over SnO2/TiO2 catalyst had the highest value, which was nearly three times as that over P25 TiO2. But it simultaneously had the lowest rate for mineralizing the objective compound. In spite that Fe3+/TiO2 catalyst behaved slightly less active than SnO2/TiO2 for degradation of benzene, the mineralization rate over Fe3+/TiO2 was the highest one among the prepared catalysts.     

The effect of solution pH and peroxide in the TiO2-induced photocatalysis of chlorinated aniline

Chlorinated anilines are frequently used in the industry as starting materials for chemical synthesis. This type of compounds can end up as pollutants in wastewater. 2-Chloroaniline (2-ClA) was selected irradiating under monochromatic UV light at 300nm. The reaction rate could be enhanced by introducing low level of H(2)O(2) into the UV/TiO(2) system. Excess H(2)O(2) could not increase the HO* generation but retarded the reaction rate. The pH effect was also investigated in UV/TiO(2) and UV/TiO(2)/H(2)O(2) systems. All the experimental results show that pH is a sensitive parameter to the rate of degradation. Low reaction rate at acidic pH could be accounted by the dark adsorption test which has also proven the photocatalysis of TiO(2) may contribute to a two-step process: (1) 2-ClA pre-adsorbed onto TiO(2) and (2) photoexcitation of TiO(2). At high pH, rate enhancement could be observed at UV/TiO(2) system because of the increase generation of HO*. However, the introduction of H(2)O(2) slowdown the decay rate at such alkaline medium.     

溶胶-凝胶法制备TiO2粉体及其光催化性能研究

以钛酸丁酯为前驱物,无水乙醇为溶剂,采用溶胶-凝胶法制备了TiO2粉体,并采用紫外分光光度计、XRD等表征手段对TiO2的粒度、晶型结构进行了表征,分析了煅烧温度、TiO2晶型比例、溶液初始pH值等因素对TiO2结构性能及光催化活性的影响.结果表明:TiO2的锐钛矿晶型与金红石晶型的转相温度为700 ℃左右;采用溶胶-凝胶法制备TiO2时,控制溶液的pH值为4,煅烧温度为600 ℃,所得产物晶型全部为锐钛矿;当无水乙醇与钛酸丁酯的体积比为10:1时,产物的粒径为617 nm;且当配制溶液pH值为4,煅烧温度为600℃条件下,煅烧时间为40~60 min时,所制备TiO2的光催化效果较好,降解率较高;当光催化体系的pH值为9、以质量浓度为10 mg/L的亚甲基兰溶液浸泡2 h,TiO2的用量为0.25 g/L时,产物的降解率高达95.3%.     

The effect of microwave-assisted for photo-catalytic degradation of rhodamine B in aqueous nano TiO2 particles dispersions

The photo-catalytic decomposition of rhodamine B was examined in aqueous nano TiO2 particles dispersions to assess effects of the microwave radiation assisted photo-catalytic process driven by UV radiation. The results of photo-catalytic degradation of rhodamine B showed that the decomposition rate increased with the microwave intensity, UV intensity, TiO2 particle dosages and the circulating fluid velocity. Addition of oxygen gas in the photo-catalytic degradation of rhodamine B increased the reaction rate. The effect of addition of H2O2 was not significant when photo-catalysis was used without additional microwave radiation or when microwave was irradiated without the use of photo-catalysts. When H2O2 was added under simultaneous use of photo-catalysis and microwave irradiation, however, considerably higher degradation reaction rates were observed. This study demonstrates that the microwave irradiation can play a very important role in photo-catalytic degradation.     

Photooxidative N-de-ethylation of anionic triarylmethane dye (sulfan blue) in titanium dioxide dispersions under UV irradiation

The TiO(2)-mediated photocatalysis process has been successfully applied to degradation of dye pollutants. Our results indicate that the TiO(2) surface is negatively charged, and the sulfan blue (SB) adsorbs onto the TiO(2) surface through the positive di-ethylamino groups while the TiO(2) surface is positively charged and the SB adsorbs onto the TiO(2) surface through the negative sulfonyl groups. In order to obtain a better understanding of the mechanistic details of this TiO(2)-assisted photodegradation of the SB dye with UV irradiation, five intermediates of the processes were separated, identified, and characterized by the HPLC-ESI-MS technique, which included a positive- and negative-ion mode. The results indicated that the N-de-ethylation process continues until the N-de-ethylated SB dye is completely formed. The probable photodegradation pathways were proposed and discussed. The reaction mechanisms of UV/TiO(2) proposed in this study should be useful for future applications of the technology to the decolorization of dyes.     

银掺杂TiO2光催化剂的制备及光催化性能研究

采用溶胶-凝胶法,以钛酸四丁酯、硝酸银为原料制备了不同银含量掺杂TiO2光催化剂,并以TG-DTA、XRD、TEM对样品进行了表征,XRD结果显示,掺杂银TiO2光催化剂为锐钛矿型,银掺杂量较低时,银均匀分布在TiO2的表面,在掺杂量为4%时,出现银的团聚。光催化亚甲基蓝结果表明,银掺杂TiO2光催化剂比未掺杂TiO2降解率明显提高,在2%银掺杂TiO2光催化剂用量为25mg,pH值为6～8,降解时间为120min,降解率可达93%。     

纳米Cu2+/TiO2抗菌膜对禽流感病毒(H9N2)的灭活效应

利用病毒滴度测定和MDCK细胞电镜观察法,初步探讨了在365nm的黑光灯(UV)照射下,纳米Cu2+/TiO2抗菌膜对禽流感病毒(H9N2)的光催化灭活效应,并分别考察了UV强度、UV照射时间以及H9N2病毒量对H9N2病毒光催化灭活效应的影响.实验结果表明,在365nm黑光灯的照射下,纳米Cu2+/TiO2抗茵膜对H9N2病毒具有显著的灭活效应,在UV强度为0.5mW/cm2、UV照射时间为2.5h、病毒量为0.1ml时,H9N2病毒的灭活率达到了100%.研究结果表明,纳米Cu2+/TiO2抗菌膜在抑制禽流感(H9N2)病毒在环境媒介中的扩散与传播方面有潜在的应用价值.     

Photocatalytic properties of silver nanoparticles decorated nanobranched TiO2 nanofibers

In this study, nanobranched TiO2 nanofibers and silver loaded nanobranched TiO2 nanofibers were prepared by electrospinning technique followed by TiCl4 aqueous solution treatment and silver photodeposition method. Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the products. X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS) were conducted on the samples to study their chemical composition as well as crystallographic structure. The photocatalytic activities of these produced nanofibers were examined with two organic dyes, methylene blue and methyl orange, under ultraviolet (UV) light irradiation. The effect of nanobranches and silver modification on TiO2 nanofibers was revealed in the photocatalysis process. The photocatalytic degradation rates of silver loaded on nanobranched TiO2 nanofibers were 1.6 and 1.7 times as that of pure TiO2 nanofibers in the presence of methylene blue and methyl orange, respectively, which indicated silver nanoparticles combined nanobranches modified on the surface of TiO2 nanofibers could enhance the photocatalytic ability.     

Comparison of several advanced oxidation processes for the decolorization of Reactive Red 120 azo dye in aqueous solution

In this study UV/TiO2, electro-Fenton (EF), wet-air oxidation (WAO), and UV/electro-Fenton (UV/EF) advanced oxidation processes (AOPs) have been applied to degrade Reactive Red 120 (RR120) dye in aqueous solution. The most efficient method on decolorization and mineralization of RR120 was observed to be WAO process. Photocatalytic degradation of RR120 by UV/TiO2 have been studied at different pH values. At pH 3 photocatalytic degradation kinetics of RR120 successfully fitted to Langmuir-Hinshelwood (L-H) kinetics model. The values of second order degradation rate (k") constant and adsorption constant (K) were determined as 4.525 mg L(-1) min(-1) and 0.387 L mg(-1), respectively. Decolorization efficiency observed in the order of WAO > UV/TiO2 = UV/EF > EF while WAO > UV/TiO2 > UV/EF > EF order was observed in TOC removal (mineralization). For all AOPs, it was found that degradation products in reaction mixture can be disposed safely to environment after 90 min treatment.     

Photocatalytic degradation of Direct Red 23 dye using UV/TiO2: Effect of operational parameters

In this study, the photocatalytic degradation of Direct Red 23 (Scarlet F-4BS) was investigated in UV/TiO2 system. The effect of catalyst loading and pH on the reaction rate was ascertained and optimum conditions for maximum degradation were determined. The results obtained showed that acidic pH is proper for the photocatalytic removal of Direct Red 23. In addition, the effects of several cations (Cu2+, Al3+, Cr3+, and Sn4+) and anions (BiO3(-), SO4(2-), and CN(-)) and C2H5OH were examined in this photocatalytic process. On the order hand, three types of catalysts (Fe2O3, SnO2, and ZnO) were compared with TiO2. After 90 min reaction, the relative decomposition order established was UV/TiO2>UV/SnO2>UV/Fe2O3>UV/ZnO.     

Synthesis of a CNT-grafted TiO(2) nanocatalyst and its activity triggered by a DC voltage

Carbon nanotube (CNT)-grafted TiO(2) (CNT/TiO(2)) was synthesized as an electrically conductive catalyst that exhibits redox ability under electrical excitation besides ultraviolet (UV) irradiation. The CNT/TiO(2) material was synthesized by a two-step process. Ni nanoparticles were photodeposited onto TiO(2) first. The Ni nanoparticles then served as seeds for the growth of CNTs using the chemical vapor deposition (CVD) of C(2)H(2). The CNT/TiO(2) nanocomposite exhibits strong oxidation activity toward NO gas molecules via both photocatalysis under UV irradiation and electrocatalysis under a DC?voltage of 500?V in dark conditions.     

Capability of coupled CdSe/TiO(2) for photocatalytic degradation of 4-chlorophenol

The photocatalytic process using TiO(2) and coupled semiconductor in the photodegradation reaction of 4-chlorophenol (4-CP) was investigated. Nanosized titanium dioxide powder was synthesized via the sol-gel procedure and modified via the coupled photocatalysts. The microstructural and chemical properties of TiO(2) and coupled CdSe/TiO(2) were also examined. For CdSe/TiO(2) samples, the specific surface area was 7.0 m(2)/g and the deposition proportion of CdSe was approximately 27.6%. In the photocatalysis results, higher photodegradation efficiency of 4-CP was observed at higher pH values. In the UV 254 nm system, the degradation efficiency of 4-CP and TOC with sol-gel produced TiO(2) (TiO(2)(SG)) powder was higher than with commercial TiO(2)(RdH) powder. For the coupled semiconductor system (CdSe/TiO(2)), the apparent first-order rate constants were 1.35 x 10(-2), 4.33 x 10(-2), 2.0 x 10(-3) and 1.9 x 10(-3)min(-1) at the conditions of pH 7 (254 nm), pH 11 (254nm), pH 7 (365 nm), and pH 11 (365 nm). The disappearance of 4-CP under CdSe/TiO(2)(RdH) photoreaction at pH 7 and 365 nm condition is better than that of TiO(2)(RdH) system, with 30% versus 22% 4-CP reduction in 180 min. In the same condition, CdSe/TiO(2)(RdH) provided more photomineralization efficiency than that of TiO(2)(RdH) in terms of TOC reduction. Both 4-CP and TOC reduction were significant for systems illuminated at 254 nm. Considering the direct photolysis effect at 254 nm where 4-CP reduction is near 100% and TOC removal is nil, CdSe/TiO(2)(RdH) exhibits a 50% photomineralization efficiency and a nearly four times faster reaction rate than the single TiO(2)(RdH) semiconductor.