Oxidation of triclosan by ferrate: reaction kinetics, products identification and toxicity evaluation

The Crystal Violet (CV) dye represented one of the major triphenylmethane dyes used in textile-processing and some other industrial processes. Various metals doped titanium dioxide (TiO(2)) photocatalysts have been studied intensively for the photodegradation of dye in wastewater treatment. In order to understand the mechanistic detail of the metal dosage on the activities enhancement of the TiO(2) based photocatalyst, this study investigated the CV photodegradation reactions under UV light irradiation using a Pt modified TiO(2) photocatalyst. The results showed that Pt-TiO(2) with 5.8% (W/W) Pt dosage yielded optimum photocatalytic activity. Also the effect of pH value on the CV degradation was well assessed for their product distributions. The degradation products and intermediates were separated and characterized by HPLC-ESI-MS and GC-MS techniques. The results indicated that both the N-de-methylation reaction and the oxidative cleavage reaction of conjugated chromophore structure occurred, but with significantly different intermediates distribution implying that Pt doped TiO(2) facilitate different degradation pathways compared to the P25-TiO(2) system.     

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 polycyclic aromatic hydrocarbons on soil surfaces using TiO(2) under UV light

The photocatalytic degradation of phenanthrene (PHE), pyrene (PYRE) and benzo[a]pyrene (BaP) on soil surfaces in the presence of TiO(2) using ultraviolet (UV) light source was investigated in a photo chamber, in which the temperature was maintained 30 degrees C. The effects of various factors, namely TiO(2), soil pH, humic acid, and UV wavelength, on the degradation performance of polycyclic aromatic hydrocarbons (PAHs) were studied. The results show that photocatalytic degradation of PAHs follows the pseudo-first-order kinetics. Catalyst TiO(2) accelerated the photodegradation of PHE, PYRE and BaP significantly, with their half-lives being reduced from 533.15 to 130.77h, 630.09 to 192.53h and 363.22 to 103.26h, respectively, when the TiO(2) content was 0.5%. In acidic or alkaline conditions, the photocatalytic degradation rates of the PAHs were greater than those in neutral conditions. Humic acid significantly enhanced the PAH photocatalytic degradation by sensitizing radicals capable of oxidizing PAHs. Photocatalytic degradation rates of PYRE and BaP on soil surfaces with 2% TiO(2) were different at UV irradiation wavelengths of 254, 310 and 365nm, respectively. The synergistic effect of UV irradiation and TiO(2) catalysis was efficient for degradation of PAHs in contaminated soil.     

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.     

Optimized photocatalytic degradation of Alcian Blue 8 GX in the presence of TiO2 suspensions

The photocatalytic degradation of Alcian Blue 8 GX, a cationic copper phthalocyanine dye, has been investigated in aqueous suspensions containing the commercial catalyst TiO(2) P-25. The photodegradation of the organic molecule follows approximately a pseudo-first kinetic order, according to the Langmuir-Hinshelwood model. The effect of catalyst concentration, pH of the initial solution and the H(2)O(2) concentration upon the reaction rate was ascertained. It was shown that the photocatalytic degradation reaction can be mathematically described as a function of parameters such as pH, H(2)O(2) concentration and irradiation time, being modeled by the use of the response surface methodology. Optimized values for oxidizing agent, concentration, pH and UV exposure time for the studied system were determined.     

Enhanced TiO2 photocatalytic degradation of bisphenol E by beta-cyclodextrin in suspended solutions

Enhancement of beta-cyclodextrin (beta-CD) on TiO(2) photocatalytic degradation of bisphenol E (BPE, bis(4-hydroxyphenyl)ethane) was investigated under a 250 W metal halide lamp (lambda> or =365 nm) in this work. In the system of photocatalytic degradation of BPE, the photodegradation rate of BPE in aqueous solutions containing beta-CD and TiO(2) was obviously faster than that in aqueous solutions containing only TiO(2). After 40 min of irradiation, beta-CD could increase the photodegradation efficiency by about 26% for 10 mg l(-1) BPE in the UV-vis/TiO(2) system and the photodegradation of 2.5-20.0 mg l(-1) BPE in aqueous solutions was found to follow pseudo-first-order law and the adsorption constant and the reaction rate constant of BPE in the system containing beta-CD and TiO(2) are obviously higher than those in the system containing only TiO(2), the influence factors on photodegradation of BPE were studied and described in details, such as beta-CD concentration, pH, BPE initial concentration and gas medium. The formation of CO(2) as a result of mineralization of BPE was observed during the photodegradation process. After 120 min of irradiation, the mineralization efficiency of BPE reached 61% in the presence of beta-CD, whereas mineralization efficiency was only 23% in the absence of beta-CD. The enhancement of photodegradation of BPE could be dependent on the enhancement of adsorption of BPE on TiO(2) surface and moderate inclusion-depth of BPE in the beta-CD cavity.     

Preparation of re-usable photocatalytic filter for degradation of Malachite Green dye under UV and vis-irradiation

Sn(4+) doped and undoped nano-TiO(2) particles easily dispersed in water were synthesized without using organic solvent by hydrothermal process. Nanostructure-TiO(2) based thin films were prepared on flyswatter substrate, made with stainless steel, by dip-coating technique. The structure, surface and optical properties of the particles and thin films were characterized by element analysis and XRD, BET, SEM and UV/vis/NIR techniques. The photocatalytic performance of the films were tested for degradation of Malachite Green dye in solution under UV and vis-lights. The results showed that the coated flyswatter has a very high photocatalytic performance for the photodegradation of Malachite Green irradiated with UV and vis-lights. The results also proved that the hydrothermally synthesized nano-TiO(2) particles are fully anatase crystalline form and are easily dispersed in water, the coated surfaces are hydrophilic, and the doping of transition metal ion efficiently improved the degradation performance of TiO(2)-coated flyswatter. The photocatalytic performances determined at both irradiation conditions were very good and were almost similar to each other for Sn(4+) doped TiO(2)-coated flyswatter and it can be repeatedly used with increasing photocatalytic activity compared to undoped TiO(2)-coated flyswatter.     

Degradation of di-n-butyl phthalate using photoreactor packed with TiO2 immobilized on glass beads

This study evaluated the performance of a photoreactor packed with TiO2/glass, TiO2 immobilized on glass beads, initiated by UV irradiation, denoted as UV/TiO2/glass, to decompose di-n-butyl phthalate (DBP) in an aqueous solution. The photodegradation rate of DBP by this UV/TiO2/glass process was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. The experimental results of this study show that the influence of pH value of an aqueous solution to reaction rate was negligible at the pH values 4.5-9. The effect of cations on the photodegradation rate of DBP reveals that the larger the charge and size of cations contained, the more the inhibition of reaction rate increased. The UV/TiO2/glass process yielded a 75% degradation efficiency of DBP with initial concentration of 5 mg L(-1) at 80 min reaction time.     

射频磁控共溅射制备光催化Ag-TiO2薄膜

采用射频磁控共溅射法制备Ag-TiO2复合薄膜,通过控制Ag靶的溅射时间可调节Ag与TiO2的比例.所制备的Ag-TiO2薄膜为锐钛矿结构.通过紫外光照降解亚甲基蓝溶液和循环伏安法研究Ag-TiO2薄膜光催化及光电化学特性.实验结果表明:掺1.5% Ag的Ag-TiO2薄膜在紫外光照射下能增强亚甲基蓝溶液的降解并得到更大的光生电流.这种光催化的增强主要是由于光生电子-空穴对的复合被抑制的结果.     

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.     

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.     

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.     

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.     

TiO2 mediated photocatalytic degradation studies of Reactive Red 198 by UV irradiation

Photocatalytic degradation of an aqueous solution of azo dye (Reactive Red 198) used in textile industries by UV irradiation was investigated. The effect of initial dye concentration, TiO(2) loading, pH and H(2)O(2) on degradation rate was ascertained and optimized conditions for maximum degradation were determined. The kinetics of photocatalytic degradation was found to follow a pseudo-first order according to Langmuir-Hinshelwood model. The degradation experiment under optimized reaction conditions was investigated under sunlight.     

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.     

二氧化钛催化光降解聚对苯二甲酸乙二酯的研究

利用原位聚合法合成PET/TiO2复合材料.通过分析PET/TiO2复合薄膜在紫外光降解过程中的质量和表面形态的变化情况,研究了锐钛矿型二氧化钛对PET光氧化降解性能的影响.结果说明,在试验范围内,在253.9nm的紫外光照射的光降解实验中,锐钛矿型TiO2的含量越高,PET/TiO2复合薄膜的质量损失率就越高;同时,紫外光照射试样288h之后,由SEM照片发现复合材料表面损伤程度也随着TiO2含量的升高而越发严重.这说明,锐钛矿型TiO2对PET的光氧化降解具有催化作用,而且含量越高催化作用就越强.     

Role of oxygen active species in the photocatalytic degradation of phenol using polymer sensitized TiO2 under visible light irradiation

The role of dissolved oxygen, and of active species generated by photo-induced reactions with oxygen, in the photocatalytic degradation of phenol was investigated using polymer [poly-(fluorene-co-thiophene) with thiophene content of 30%, so-called PFT30] sensitized TiO2 (PFT30/TiO2) under visible light irradiation. The photoluminescent (PL) quantum yield of PFT30/TiO2 was about 30% of that of PFT30/Al(2)O(3), proving that electron transfer took place between the polymer and TiO2. The result that photocatalytic degradation of phenol was almost stopped when the solution was saturated with N(2) proved the importance of O(2). Addition of NaN(3), an effective quencher of singlet oxygen ((1)O(2)), caused about a 40% decrease in the phenol degradation ratio. Addition of alcohols caused about a 60% decrease in the phenol photodegradation ratio, indicating that the hydroxyl radicals (OH), whose presence was confirmed by electron spin resonance (ESR) spectroscopy, was the predominant active species in aqueous solution. In anhydrous solution, singlet oxygen ((1)O(2)) was the predominant species. These results indicate that oxygen plays a very important role in the photocatalytic degradation of phenol.     

Preparation of Fe3+-doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation

Fe3+-doped TiO2 (Fe-TiO2) porous microspheres were prepared by controlled hydrolysis of Ti(OC4H9)4 with water generated "in situ" via an esterification reaction between acetic acid and ethanol, followed by hydrothermal treatment. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectrum, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption-desorption methods. All of the undoped TiO2 and Fe-TiO2 samples exclusively consist of primary anatase crystallites, which further form porous microspheres with diameters ranging from 150 to 500 nm. The photocatalytic activity of Fe-TiO2 catalysts was evaluated from the photodegradation of methyl orange (MO) aqueous solution both under UV and visible light irradiation. Fe3+ doping effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.1 and 0.2%, respectively. The photocatalytic mechanisms of Fe-TiO2 catalysts were tentatively discussed.     

Photocatalytic degradation of 2,4-dinitrophenol

Contamination of the food supply from agricultural waste is an increasing concern worldwide. Numerous hazardous chemicals enter the environment from various industrial sources daily. Many of these pollutants, including 2,4-dinitrophenol (2,4-DNP), are water soluble, toxic, and not easily biodegradable. The solar photocatalytic degradation of 2,4-DNP was investigated in a solution of titanium dioxide (TiO(2)) that was prepared to be an optically clear aqueous solution of nanosized particles of TiO(2). In order to achieve optimal efficiency of the photodegradation, the effects of light intensity and pH were conducted. All experiments were carried out in a batch mode. At a pH of 8, maximum removal of 70% of 2,4-DNP was achieved within 7h of irradiation time. The nearly homogeneous solution of 5.8nm TiO(2) particles, size determined by XDS, were very effective in the photocatalytic degradation of 2,4-DNP.     

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.