Heterogeneous photocatalytic degradation of monochlorobenzene in water

This investigation evaluated the photocatalytic degradation of monochlorobenzene (MCB) in an aqueous TiO(2) suspension. In accordance with the experimental results, the degradation of MCB was a function of the initial substrate concentration, incident light intensity, and TiO(2) dosage. However, the solution pH had insignificant effect on the degradation efficiency. The heterogeneous photocatalytic degradation of MCB followed the Langmuir-Hinshelwood kinetics. The adsorption coefficient of MCB (K) and the observed degradation rate constant (k) were calculated as 13.4 mM(-1) and 0.0054 mM min(-1), respectively. In addition, a 0.255 dependency of the initial degradation rate on the light intensity revealed the considerable adverse effect of e(-)-h(+) pair recombination. Both mineralization and dechlorination occurred during the photocatalytic degradation of MCB. Under the operating condition of initial MCB concentration of 0.1mM, light intensity of 5.68 microEinsteins(-1), TiO(2) dosage of 1.0 g L(-1), and solution pH of 7, about 93.7% of MCB was mineralized after 240 min of irradiation. Nevertheless, 64.3% of the stoichiometric amount of Cl(-) ions was released into the bulk solution. The simulation results derived from the X-ray photoelectron spectroscopy (XPS) analysis was suggested that the interaction between Cl(-) ions and TiO(2) surface tended to lower the released amount of Cl(-) ions.     

Photocatalytic oxidation of VX simulant 2-(butylamino)ethanethiol

Photocatalytic oxidation of 2-(butylamino)ethanethiol (BAET) was undertaken in aqueous suspension of TiO2 Hombikat UV 100 and Degussa P25 under different initial reaction conditions in order to determine the best parameters for the fastest mineralization of the substrate. BAET is considered to be a simulant for the VX chemical warfare agent. The application of ultrasound had only a small positive effect on the BAET photocatalytic degradation. The highest mineralization rate of 0.433 mg/(l min) was found in unbuffered TiO2 Degussa P25 suspension with initial pH value of about 9.4, TiO2 concentration 500 mg/l and the initial BAET concentration 1000 mg/l. Decreasing of the initial solution pH to 6.1 or below stops the mineralization of BAET while increasing of pH to about 11 drastically changed the degradation profile. At this initial pH, the first 100 min of reaction led to only oxidation of sulfur moiety and organic intermediates accumulated in the solution. Thereafter, mineralization of the products started. The main detected volatile product was butyl aldehyde and the main polar one was 2-(butylamino) acetic acid. In the case of TiO2 Hombikat UV 100, conversion of TOC at initial pH 11 exceeded that at initial pH 9.1. For Degussa P25, the starting pH 9.4 was the best for TOC conversion. The results can be used for treatment of water from pollutants with aliphatic nitrogen and sulfur atoms.     

Photocatalytic degradation of 3,4-dichlorophenylurea in aqueous gold nanoparticles-modified titanium dioxide suspension under simulated solar light

The TiO(2) modified with nanosized gold particles was prepared by deposition-precipitation at pH 7 and calcination in air at various temperatures up to 973 K. The materials were characterized by transmission electron microscope, X-ray diffraction spectrometry, and atomic absorption spectroscopy. The highest photocatalytic efficiency was obtained at the calcination temperature of 873 K. The decrease in 3,4-dichlorophenylurea concentration follows first order kinetics with a half life of 36.6 ± 2.0 min in 100 mg L(-1) of 0.83 wt% Au/TiO(2). Fifteen degradation products were identified using LC/MS/MS and IC. Degradation pathway was proposed on the basis of the observed transformation products.     

Surface modification of nanometer size TiO2 with salicylic acid for photocatalytic degradation of 4-nitrophenol

The efficiency of photocatalytic reactions was limited by the wide band-gap of TiO(2) and the high degree of electron-hole recombination inherent in photocatalytic process, as well as by the limited adsorption capability of photocatalysts. In order to increase the overall efficiency, the surface of nanometer size TiO(2) was simply and fast modified by chemical adsorption in saturated solution of salicylic acid. A stable, light yellow surface complex was formed quickly, which has obvious absorption in the region from 320 to 420 nm. Through surface modification, the adsorption efficiency of 4-nitrophenol by TiO(2) was enhanced from 42 to 84%. The photocatalytic efficiency was tested on the degradation of 4-nitrophenol. The influences of catalyst and its dosage, pH value, and 4-nitrophenol concentration on the degradation were investigated. Under such photodegradation conditions as initial pH 4.0, 4-nitrophenol 5 mg l(-1), catalyst 100 mg, and irradiation time 160 min with 160 W high-pressure mercury lamp, the degradation efficiency of 4-nitrophenol by TiO(2) was increased from 39.5 to 79.3% after surface modification, and furthermore, the degradation efficiency could be enhanced to 91.1% if the concentration of 4-nitrophenol was not more than 1 mg l(-1). Compared with the pure TiO(2), surface modification led not only to improve the surface coverage of 4-nitrophenol, but also to increase the light utilization. Both of these factors were crucial for the photocatalytic activity of heterogeneous photocatalysis, especially for photodegradation of aromatic pollutants.     

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%.     

Photolytic (UVC) and photocatalyic (UVC/TiO2) decomposition of pyridines

The degradation of 2-chloropyridine (2-CPY) and its degradation primary product 2-hydroxypyridine (2-HPY) was studied by means of ultraviolet (UV) irradiation at 254nm. Photolytic and photocatalytic experiments were conducted on 2-CPY and 2-HPY aqueous solutions in a batch reactor with internal recycle in laminar and turbulent conditions at 50 degrees C in a closed but not airtight system with and without additional aeration, at solution ambient pH and at controlled pH conditions, with use and in the absence of radical scavenger. The solution volume was 0.4L and initial substrate concentrations were approximately 2.6mmol/L (0.25-0.3g/L depending on the substrate). Where applicable 1g/L TiO(2) (P-25) was used, suspended in the liquid in a form of turbulent slurry or using a glass tube around the UV-lamp on which a fixed TiO(2) catalytic layer had been deposited. At the aforementioned conditions 2-CPY readily degrades photolytically, the catalytic path having very little influence. In all cases 2-CPY produces 2-HPY which further degrades to other products. Aeration, pH and the presence of catalyst and/or radical scavengers do not affect the rate of decomposition of 2-CPY, but have a strong influence on the further decomposition of the produced 2-HPY. 2-HPY decomposition proceeds both catalytically and photolytically following oxygen dependent and oxygen independent pathways.     

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 Congo Red by hydrothermally synthesized nanocrystalline TiO2 and identification of degradation products by LC-MS

Degradation of Congo Red (CR) dye in aqueous solutions was investigated by means of photocatalysis of TiO2 which was hydrothermally synthesized at 200 degrees C in 2 h, in anatase phase with 8 nm crystallite size. Efficiency of TiO2 in photocatalytic degradation under visible irradiation was studied by investigating the effects of amount of TiO2, irradiation time, initial CR concentration and pH. It was found that complete decolorization is achieved within 30 min of irradiation. Effects of nitrate and sulphate ions and humic acid on the degradation were also tested. The results were compared with Degussa P-25 TiO2 at the same degradation conditions. Degradation products were detected using LC-MS technique. The probable pathways for the formation of degradation products were proposed.     

Photocatalytic removal of hazardous dye cyanosine from industrial waste using titanium dioxide

In this paper, photocatalytic degradation studies of a hazardous water soluble xanthene dye cyanosine in aqueous suspensions of titanium dioxide under a variety of conditions, viz., catalyst concentration, substrate concentration, pH, temperature and electron acceptor hydrogen peroxide (H2O2) have been reported. It was observed that photocatalytic degradation by TiO2 is an effective, economic and faster mode of removing cyanosine from aqueous solution. The optimum conditions for the degradation of the dye was dye concentration 1x10(-4)M, pH 8, catalyst concentration 0.04g/L and temperature +/-30 degrees C. Chemical oxygen demand and dye absorbance of the photodegraded dye solution substantially decreased.     

Solar photocatalitycal treatment of carbofuran at lab and pilot scale: effect of classical parameters, evaluation of the toxicity and analysis of organic by-products

In this work the TiO(2) solar-photocatalytical degradation of the pesticide carbofuran (CBF) in water, at lab and pilot scale, was studied. At lab scale the evaluation of CBF concentration (14-282 μmol L(-1)) showed that the system followed a Langmuir-Hinshelwood kinetics type. TiO(2) concentration (0.05-2 g L(-1)) and initial pH (3-9) were also evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, initial pH 7.60 and 1.43 g L(-1) of TiO(2) favoured the efficiency of the process. Under optimal conditions the evolution of substrate, chemical oxygen demand, dissolved organic carbon, toxicity and organics by-products were evaluated. In the pilot scale tests, using direct sunlight, 55 mg L(-1) of CBF in a commercial formulation was eliminated after 420 min; while after 900 min of treatment 80% of toxicity (1/E(50) on Vibrium Fischeri), 80% of chemical oxygen demand and 60% of dissolved organic carbon were removed. The analysis and evolution of five CBF by-products, as well the evaluation of the treatment in the presence of isopropanol or using acetonitrile as a solvent suggest that the degradation is mainly carried out by OH radical attack. Finally, a schema depicting the main degradation pathway is proposed.     

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.     

Photocatalytic degradation of indigo carmine in aqueous solution by TiO2-coated non-woven fibres

The photocatalytic degradation of indigo carmine has been investigated in aqueous solutions using TiO2 coated non-woven fibres as photocatalyst. The experiments were carried out to investigate the factors influencing the photocatalytic degradation, such as the previous adsorption in the dark, initial concentration of dye solution, temperature, and pH. The experimental results show that adsorption is an important parameter controlling the apparent kinetic constant of the degradation. The photocatalytic degradation rate was favoured by a high concentration of solution in respect to Langmuir-Hinshelwood model. The degradation rate was pH and temperature dependent with a high degradation rate at high temperature.     

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.     

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.     

Photocatalytic degradation of pollutants from Elcogas IGCC power station effluents

The aim of this work is to improve the quality of water effluents coming from Elcogas IGCC power station (Puertollano, Spain) with the purpose of fulfilling future more demanding normative, using heterogeneous photocatalytic oxidation processes (UV/H(2)O(2)/TiO(2) or ZnO). The efficiency of photocatalytic degradation for the different catalysts (TiO(2) and ZnO) was determined from the analysis of the following parameters: cyanides, formates and ammonia content. In a first stage, the influence of two parameters (initial concentration of H(2)O(2) and amount of catalyst) on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. pH was always kept in a value >9.5 to avoid gaseous HCN formation. The degradation of cyanides and formates was found to follow pseudo-first order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The mathematical model reproduces experimental data within 90% of confidence and allows the simulation of the process for any value of parameters in the experimental range studied. Moreover, a measure of the saliency of the input variables was made based upon the connection weights of the neural networks, allowing the analysis of the relative relevance of each variable with respect to the others. Results showed that the photocatalytic process was effective, being the degradation rate of cyanides about five times higher when compared to removal of formates. Finally, the effect of lowering pH on the degradation of formates was evaluated after complete cyanides destruction was reached (10 min of reaction). Under the optimum conditions (pH 5.2, [H(2)O(2)]=40 g/l; [TiO(2)]=2g/l), 100% of cyanides and 92% of initial NH(3) concentration are degraded after 10 min, whereas 35 min are needed to degrade 98% of formates.     

Modeling electrowinning process in an expanded bed electrode

In this paper, the photocatalytic degradation of methamidophos, an organophosphorous pesticide, was investigated in aqueous solution by using TiO(2) as a photocatalyst. The degradation was studied under different conditions such as the amount of the photocatalyst, illumination time, pH of the system, reaction temperature, initial concentration, electron acceptors, metal ions and presence of anions. The results showed that the photocatalytic degradation of methamidophos was strongly influenced by these parameters. The best conditions for the photocatalytic degradation of methamidophos were obtained. The optimum amount of the photocatalyst used is 12.0g/L. The photodegradation efficiency of methamidophos increases with the increase of the illumination time. Alkaline media are favorable for the photocatalytic degradation of methamidophos. The degradation efficiency is enhanced by increasing reaction temperature, and the photodegradation efficiency decreases with the increase in the initial concentration of methamidophos. The photodegradation efficiency of methamidophos is accelerated by adding a small amount of H(2)O(2), K(2)S(2)O(8), KBrO(3), Fe(3+) or Cu(2+). There are no obvious effects on the reactions with the addition of a small amount of Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Co(2+) and Ni(2+) or adding trace amount of SO(4)(2-), Cl(-), Br(-). The possible roles of the additives on the reactions and the possible mechanisms of effect were also discussed.     

氮掺杂改性TiO_2多孔薄膜光催化降解4-硝基苯酚

本文采用溶胶-凝胶法制备了N掺杂TiO_2光催化剂,并对N掺杂TiO_2进行了改性,分别以P25、N掺杂TiO_2、改性的N掺杂TiO_2为原料,通过逐步研磨、旋转涂膜以及高温煅烧制得三种多孔薄膜,并对其进行了表征。场发射扫描电子显微镜(FESEM)观察结果显示,煅烧后薄膜呈现显著的多孔结构。以4-硝基苯酚(4-NP)溶液为目标污染物,研究紫外光下TiO_2多孔薄膜的光催化性能,确定最佳降解条件,并研究了薄膜耐用性以及三种薄膜对4-NP的光催化性能的比较。结果表明,三种多孔薄膜中,改性N掺杂TiO_2多孔薄膜光催化性能最佳,10mg/L的4-NP溶液吸附30min,在pH=2条件下180min,降解率达到了90%以上,改性N掺杂TiO_2多孔薄膜单次降解180min,循环使用4次的降解率仍接近80%,显示了薄膜具有较好的可耐用性。     

Photocatalytic degradation of Basic Red 46 and Basic Yellow 28 in single and binary mixture by UV/TiO2/periodate system

The present study deals with the investigation of photocatalytic degradation and mineralization of C.I. Basic Red 46 (BR46) and C.I. Basic Yellow 28 (BY28) dyes in single and binary solutions as a function of periodate ion concentration (IO(4)(-)), irradiation time, initial pH and initial dye concentrations. First order derivative spectrophotometric method was used for to simultaneous analysis of BY28 and BR46 in binary mixtures. Langmuir-Hinshelwood kinetic model was applied to experimental data and apparent reaction rate constant values were calculated. The apparent degradation rate constant values of BR46 were higher than those of BY28 for all experiments in single dye solutions. On the other hand, the significant reductions were observed for the apparent degradation rate constant values of the BR46 in the presence of BY28 in binary solutions whereas TOC removal efficiency slightly enhanced in binary system. The highest TOC removal efficiency was obtained at pH 3.0 by adding 5mM periodate ion in to the solution in the presence of 1g/L TiO(2) for both dye solutions. After 3h illumination, 68, 76 and 75% mineralization were found for 100mg/L BY28, 100mg/L BR46 and 50+50mg/L mixed solutions, respectively.     

Development of photocatalytic TiO2 nanofibers by electrospinning and its application to degradation of dye pollutants

We have developed photocatalytic TiO2 nanofibers for the treatment of organic pollutants by using electrospinning method. We found that the optimized electrospinning conditions (electric field and flow rate) were 0.9 kV cm(-1) and 50 microL min(-1). After annealing at 550 degrees C for 30 min, we fabricated TiO2 nanofibers (average 236 nm thick) with anatase crystalline phase. To increase photocatalytic activity and effective surface area, we coated photocatalytic TiO2 particles on the TiO2 nanofibers by using sol-gel method. The degradation rate (k'=85.4x10(-4) min(-1)) of composite TiO2 was significantly higher than that (15.7x10(-4) min(-1)) of TiO2 nanofibers and that (14.3x10(-4) min(-1)) of TiO2 nanoparticles by the sol-gel method. Therefore, we suggested that the composite TiO2 of nanofibers and nanoparticles be suitable for the degradation of organic pollutants.     

Studies on TiO(2)/ZnO photocatalysed degradation of lignin

The photocatalytic degradation of lignin obtained from wheat straw kraft digestion has been investigated by using TiO(2) and ZnO semiconductors. ZnO has been found to be a better photocatalyst than TiO(2). The different variables studied, include catalyst dose, solution pH, oxidant concentration and initial concentration of the substrate. The degradation of lignin was favorable at pH 11. Optimum values of catalyst dose and oxidant concentration were found to be 1g/l and 12.2 x 10(-6) M, respectively. The degradation of the organic compound was also evaluated as COD removal and increase in the COD removal was observed with increase in degradation rate. An attempt has also been made to explore the applicability of ZnO in immobilized mode for the degradation of lignin under solar light for industrial scale application. Further the comparative evaluation of ZnO in slurry/immobilized mode has been carried out.