Parathion degradation and toxicity reduction in solar photocatalysis and photolysis.

The solar photocatalytic degradation of methyl parathion was investigated using a circulating TiO2/solar light reactor. Under solar photocatalysis condition, parathion was more effectively degraded than solar photolysis and TiO2-only conditions. With solar photocatalysis, 20 mg/L of parathion was completely degraded within 60 min with a TOC decrease of 63% after 150 min. The main ionic byproducts during photocatalysis recovered from parathion degradation were mainly as NO3-, NO2- and NH4+, 80% of the sulphur as SO4(2-), and 5% of phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and methyl paraoxon were also identified, and these were further degraded in solar photocatalytic condition. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by solar photocatalysis and photolysis. The Microtox test using V. fischeri showed that the toxicity expressed as EC50 (%) value increased from 5.5% to >82% in solar photocatalysis, indicating that the treated solution is non-toxic, but only increased from 4.9 to 20.5% after 150 min in solar photolysis. The acute toxicity test using D. magna showed that EC50 (%) increased from 0.05 to 1.08% under solar photocatalysis, but only increased to 0.12% after 150 min with solar photolysis, indicating the solution is still toxic. The pattern of toxicity reduction parallels the decrease in TOC and the parathion concentrations.     

Optimised photocatalytic degradation of a mixture of azo dyes using a TiO(2)/H(2)O(2)/UV process

The aim of the present study was to optimise the photocatalytic degradation of a mixture of six commercial azo dyes, by exposure to UV radiation in an aqueous solution containing TiO(2)-P25. Response surface methodology, based on a 3(2) full factorial experimental design with three replicates was employed for process optimisation with respect to two parameters: TiO(2) (0.1-0.9 g/L) and H(2)O(2) (1-100 mmol/L). The optimum conditions for photocatalytic degradation were achieved at concentrations of 0.5 g TiO(2)/L and 50 mmol H(2)O(2)/L, respectively. Dye mineralisation was confirmed by monitoring TOC, conductivity, sulfate and nitrate ions, with a sulfate ion yield of 96% under optimal reactor conditions. Complete decolorisation was attained after 240 min irradiation time for all tested azo-dyes, in a process which followed a pseudo-first kinetic order model, with a kinetic rate constant of approximately 0.018 min(-1). Based on these results, this photocatalytic process has promise as an alternative for the treatment of textile effluents.     

Solar degradation of Direct Blue 71 using surface modified iron doped ZnO hybrid nanomaterials

This paper reports photodegradation of Direct Blue 71 under irradiation by sunlight. We synthesized Fe:ZnO nanomaterials under mild hydrothermal conditions (P = autogenous, T = 100 °C, t = 18 h). The precursors were Fe(2)O(3) as dopant, n-butylamine as surface modifier, NaOH as mineralizer and reagent grade ZnO. The systematic experiments on the photodegradation of Direct Blue 71 were carried out by changing different effective parameters. The variables in this study were type of nanomaterials synthesized (4 types), nanomaterial dosage (0.4-1.0 g/L), contact time (30-120 min), pH (3-11), and dye concentration (20-100 ppm). The photodegradation efficiency was determined using a UV-Vis spectrophotometer. Determination of total organic carbon (TOC) amount was used to find out mineralization efficiency. Our experimental results revealed that the nanomaterials synthesized had higher efficiency compared with the reagent grade ZnO. The best efficiency was achieved at the following conditions: 1.0 g/L nanomaterials loading, 120 min contact time, pH 5, and photodegradation efficiency from more than 75 up to 99% depending upon the dye concentration.     

Ti/MCM-22/MCM-41微介孔复合材料光催化降解酸性红B模拟废水的研究

采用纳米自组装法制备了具有吸附性和光催化性的Ti/MCM-22/MCM-41微介孔复合材料,利用X射线衍射、N2吸附、扫描电镜等方法对其进行表征。将复合材料用于光催化降解酸性红B的实验,考察了催化剂用量、光照时间、pH值和染料初始浓度对光催化降解率的影响,并对光降解产物进行了紫外光谱分析。结果表明:当染料的初始浓度为50 mg/L,废水pH在6左右,催化剂投加量为0.1 g/L,光照时间120 min,酸性红B的去除率可达98%以上,光催化降解反应遵循一级反应动力学方程。降解产物的紫外光谱图表明,降解后酸性红B的两个特征吸收带消失,结构的共轭系被打破,颜色消失,说明该复合材料去除水中的酸性红B主要是通过光催化作用。     

负载型纳米TiO2光催化降解罗丹明B动力学与机理研究

采用负载型纳米TiO2/AC在流化床反应器中降解罗丹明B染料废水。研究了罗丹明B的光催化降解反应动力学与降解机理。结果表明,负载型纳米TiO2光催化降解罗丹明B过程符合一级动力学方程,降解机理首先是罗丹明B分子发色基团苯氨基、羰基键被破坏,然后是无色中间产物的逐渐降解。     

Degradation of parathion and the reduction of acute toxicity in TiO2 photocatalysis.

Photocatalytic degradation of methyl parathion was done using a circulating TiO2/UV and TiO2/solar reactor. Indoor experimental results showed that, under the photocatalysis conditions, parathion was more effectively degraded than under the photolysis and TiO2 only conditions. Parathion (38 microM) was completely degraded under photocatalysis within 90 min, and more than 80% TOC decrease after 150 minutes. The main ionic byproducts during the photocatalysis were measured, and almost complete nitrogen recovery was achieved as mainly NO3- NO2-, and NH4+, and 80% of sulfur as recovered as SO4(2)-. Organic intermediates such as nitrophenol and methyl paraoxon were also identified during the photocatalysis of parathion, and these were further degraded after 90 minutes. Microtox bioassay using Vibrio fischeri was used in evaluating the toxicity of solutions treated by photocatalysis and photolysis of parathion. The results showed that the acute toxicity expressed as EC50 almost reduced after 90 min under the photocatalysis condition whereas only 40% reduction of toxicity as EC50 was achieved in photolysis condition. The outdoor results using a TiO2/solar system were similar to the TiO2 indoor system, indicating the possibility of applying TiO2/solar system for the treatment of parathion-contaminated water.     

Degradation of recalcitrant organic contaminants by solar photocatalysis.

Biological pre-treated landfill leachates of Djebel Chakir contains some macromolecular organic substances that are resistant to biological degradation. The aim of the present work is to assess the feasibility of removing refractory organic pollutants in biological pre-treated landfill leachate by solar photocatalyse process. Leachate pollutant contents are studied to assess their contribution to leachate pollution and their treatability by solar photocatalyse process. Phenol is chosen as model of pollutants, to evaluate its removal and the efficiency of the photocatalytic system. The experiments were carried out in suspended photocatalytic reactor, using TiO2 Degussa P25, under sunlight illumination (UV-A: 15-31 W/cm2). Under optimum operational conditions, applied to single reactant (phenol), the system presents a TOC removal of 90% (the degradation follows a first-order kinetic). Based on the TOC removal, the results shows that the degradation of biological pre-treated leachate follows a zero-order kinetic. After 5 h of sunlight exposure, 74% of COT is removed. The TOC removal is the best without any correction of the pH and at the TiO2 concentration of 2.5 g/L. The photocatalytic degradation of organic contaminants as well as the formation and disappearance of the by-products were followed by GC/MS. The solar photocatalysis processes induce several modifications of the matrix leading to more biodegradable forms: all the remaining and new compounds generated after the biological pre-treatment of leachate are degraded and other types of organics appear, mainly carboxylic acid, aliphatic hydrocarbons and phtalic acids.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

Decolorization and mineralization of Oolong tea polyphenols in colored soft drink wastewater by photo Fenton reaction

The decolorization and the mineralization of the colored soft drink wastewater including Oolong tea polyphenols by the photo Fenton reaction have been investigated. The decolorization of the colored soft drink wastewater including Oolong tea polyphenols by the photo Fenton reaction could be divided into 3 phases. Just after H2O2 was added to the solution, the color of the solution immediately increased from absorbance of 0.247 to 0.711 at the wavelength of 400 nm, which was defined as the 1st phase. Subsequently the significant decolorization by the photo Fenton reaction occurred at the 2nd phase. Finally, complete decolorization (the color attributed to the color of Fe3+) could be achieved in 180 min at the 3rd phase. The instantaneous and considerable color increase at the 1st phase could be attributed to the formation of intermediate colored compounds like quinones and soluble iron complexes produced by the Fenton reaction. About 95% mineralization of model colored soft drink wastewater with 229 mg L(-1) initial TOC concentration was achieved after 165 min.     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

Noble metal modified titania catalysts in the degradation of reactive black 5: a kinetic approach

The photocatalytic degradation of Reactive Black 5 (RB 5), a di-azo dye was investigated over M/TiO2 (M = Ag, Au and Pt) photocatalysts irradiated with UV and visible light. TiO2 was prepared by sol-gel technique (Syn-TiO2). Photodeposition of metal salt precursors over Syn-TiO2 was carried out so as to obtain 1 wt% of M/TiO2 catalysts. The photodecolourization and photodegradation reactions were also compared with commercial TiO2 (Degussa P25) catalyst. Kinetic studies for the decolourization of RB 5 showed that it followed pseudo first order. Recycling of catalysts was performed to check the economic feasibility of the photocatalytic process. In order to check the applicability of M/TiO2 catalyst in the treatment of industrial effluent, real textile effluent was collected from an industry and subjected to photodegradation and the results are presented. Enhanced activity of M/TiO2 catalyst under visible light irradiation highlights its importance in the field of photocatalysis.     

Application of a sequential batch reactor system for textile dyes degradation: comparison between azo and phthalocyanine dyes.

Photocatalysis on supported TiO2 was combined with aerobic biological treatment in a sequential batch reactor to compare the degradation of two textile dyes: a blue azo dye (DR KBL CDG) and a green phthalocyanine dye (DR K4GN). Three reactors were run in parallel. SBR1 was used as a reference and was fed with urban wastewater only. SBR2 and SBR3 were fed with the same urban wastewater combined with pretreated (for SBR2) and non-pretreated (for SBR3) dye solution. For an azo dye concentration of 12 mg/L decolouration yields of 78 and 27% were achieved, respectively, in SBR2 and SBR3. For the phthalocyanine dye, the decolouration yields decreased to 24 and 15%, respectively. Concerning COD removal it decreases for both dyes with and without pretreatment, when the dye concentration increases. Although a detrimental effect on biomass could be observed, bacteria were able to cope with the inhibitory effect of the dyes.     

Decolorization of anthraquinone dye Reactive Blue 19 by the combination of persulfate and zero-valent iron

Decolorization of anthraquinone dye Reactive Blue 19 (RB19) with sulfate radicals generated in situ from persulfate and zero-valent iron (ZVI) was investigated. The effects of initial solution pH, initial concentration of RB19, ZVI and persulfate, reaction temperature and common dissolved anions were studied. 100% color removal efficiency and 54% TOC removal efficiency were achieved in 45 min with an initial RB19 concentration of 0.1 mM under typical conditions (pH 7.0, 0.8 g L(-1) ZVI, 10 mM persulfate and 30 C). The decolorization efficiency of RB19 increased with higher iron dosage, higher initial persulfate concentration, and higher reaction temperature. It is also an acid driven process. The decolorization process followed pseudo-first order kinetics and the activation energy was 98.1 kJ mol-1. RB19 decolorization was inhibited by common dissolved anions such as CL-, NO3-, H2PO4- and HCO3- since they reacted with sulfate radicals that retarded the oxidation process. The experiment demonstrated that the combination of persulfate and ZVI was a promising technology for the decolorization of dye wastewater.     

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.     

Quantum efficiencies of the photo-Fenton degradation of atrazine in water

An experimental work in a well-stirred batch recycling reactor for the photo-Fenton degradation of atrazine in water is presented. A study of the quantum efficiency is performed to assess the effectiveness of the photo-Fenton process on the atrazine degradation and total organic carbon (TOC) mineralization. Apparent and absolute quantum efficiencies of degradation and mineralization of an atrazine-based commercial herbicide are determined under different experimental conditions. Higher apparent efficiencies were found for both atrazine degradation and TOC mineralization when the ferric ion and hydrogen peroxide concentrations are increased. Because of the well known stability of the triazine ring, atrazine was not completely mineralized by the photo-Fenton process. However, a TOC reduction of 40% was achieved, being 62.5% of the maximum value that can be reached.     

Removal of a synthetic dye “Direct Fast Blue B2RL” via adsorption and photocatalytic degradation using low cost rutile and Degussa P25 titanium dioxide

Removal of a commercial dye (Direct Fast Blue B2RL) has been successfully achieved by rutile TiO₂ (R) via adsorption followed by the UV/photocatalytic degradation. The data of adsorption and photocatalytic processes was compared to that obtained using the commonly widespread Degussa P25 TiO₂ (D). The parameters which affect both adsorption and photocatalytic processes such as specific surface area (S_BET), particle size, zeta potential, bandgap as well as the effect of pH on the dye structure have been measured and illustrated. Multi ionic forms were obtained for B2RL at different pH values due to the protonation/deprotonation of the functional groups. In both TiO₂ types, experimental data for the adsorption processes agreed with Langmuir and Freundlich models in both acidic and neutral media. Whereas, due to repulsion forces, the data fitted only Langmuir model in basic medium suggesting the absence of multilayers. D showed higher adsorption capacities toward B2RL than R in acidic and neutral media. The great difference in the values for the maximum amount of B2RL bound per unit weight of TiO₂ (q_m) between R and D was mainly obtained at low pH, which is not required in the photocatalytic degradation processes. At low pH's, the super tendency of B2RL toward TiO₂ surface adsorption blocked the photoactive sites in TiO₂ surface.The photocatalytic degradation reaction of different ionic forms of B2RL in the two types of TiO₂ has been studied in both solid and liquid systems. It has been concluded that the main photodegradation of B2RL takes place at the surface of the catalyst and the rate constant (k) decreases in solid and liquid systems as follows:- in R the order is pH 12 > pH 5.7 (neutral) > pH 2, while in D the order is pH 5.7 > pH 12 > pH 2.COD analysis confirmed the complete mineralization of B2RL via photocatalytic degradation using both R and D. The influence of different parameters affecting the photocatalytic degradation process such as, initial dye concentration, TiO₂ dosage, and light intensity have been studied.Durability of rutile TiO₂ and Degussa P25 was also investigated. R and D possessed good performance after repeated running in the photocatalytic degradation system.     

Photocatalytic degradation of p-nitrophenol by zinc oxide particles

The degradation of p-nitrophenol (PNP) by ZnO particles has been studied. With increasing PNP loading the degradation rate decreased. The mineralization of PNP was rather slow compared with the degradation. With a decrease in particle diameter or an increase in surface area, the degradation rate significantly increased. The degradation capability with solar irradiation was found to be superior to UV light irradiation. It was found that 30 mg L(-1) of PNP was completely degraded by solar light with the accumulated UV light of around 23 kJ L(-1) at ZnO dosage of 5 g L(-1). The degradation PNP by ZnO with UV light or solar light was faster than that by TiO(2).     

Photodegradation of 4-chloronitrobenzene in the presence of aqueous titania suspensions in different gas atmospheres

The photocatalytic degradation of 4-chloronitrobenzene (4-CNB) was carried out using Degussa P25 TiO(2) as photocatalyst in three different gas atmospheres: nitrogen, oxygen, and ozone. The total organic carbon (TOC) and inorganic anions including chloride, nitrite, and nitrate anions were measured to monitor the mineralization processes, while the degradation of 4-CNB and the formation of intermediates were followed by liquid chromatography-mass spectrometry (LC/MS). Results showed that the photocatalytic efficiency followed the order of TiO(2)/UV/N(2) < TiO(2)/UV/O(2) < TiO(2)/UV/O(3), which was further proved by evaluating the reaction activities using electron paramagnetic resonance (EPR) spin trapping technique. Chlorine atom, nitro group and hydrogen atom of the benzene ring could be displaced by hydroxyl radical (?OH) leading to the formation of chloride, nitrite (III) anions and a variety of phenols, then the nitrite (III) anions were further oxidized to nitrate (V) anions. 4-Nitrophenol and 5-chloro-2-nitrophenol were identified and quantified in both of the TiO(2)/UV/N(2) and TiO(2)/UV/O(2) processes while no aromatic intermediates were monitored in the process of TiO(2)/UV/O(3).     

Photocatalytic oxidation of methyl ethyl ketone over sol-gel and commercial TiO2 for the improvement of indoor air.

This work focuses on the photocatalytic oxidation of gaseous methyl ethyl ketone chosen as a typical indoor air pollutant. Two types of TiO coatings were prepared and deposited on glass plates: one using the commercial Degussa P25 TiO2 and the other one by sol-gel method. The first objective of this study was to compare different ways of preparing thin films of sol-gel TiO2 coated on glass plates, taking into account their general aspect and their photocatalytic efficiency. Several parameters were tested, such as the stabilising agent, the glass type of the support, the number of coatings and the calcination temperature. One of the synthesised materials was then kept to carry out the following study. The study aimed to assess the influence of TiO2 coating types on the effect of water vapour. This was achieved by performing MEK photocatalytic degradation kinetics under two levels of humidity at a fixed temperature. Experimental results were then modelled by the Langmuir-Hinshelwood equation. The obtained parameters gave specific trends in function of the considered catalyst. The second part of this work was to identify MEK degradation byproducts during its photocatalytic oxidation. The main detected intermediate was acetaldehyde, followed by methyl formate. A MEK degradation pathway was then proposed.     

Waste fly ash–ZnO as a novel sunlight-responsive photocatalyst for dye discoloration

Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future. In this study, a novel photocatalyst, partly derived from waste material from the coal industry, was developed. Fly ash hybridized with ZnO (FA—Zn) was synthesized as a potential photocatalyst for dye discoloration. The synthesized photocatalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and ultraviolet—visible/near infra-red spectroscopy. The photocatalytic activity was examined with the discoloration of methylene blue used as synthetic dye wastewater. All the experiments were performed in direct sunlight. The photocatalytic performance of FA—Zn was found to be better than that of ZnO and the conventionally popular TiO₂. The Langmuire—Hinshelwood model rate constant values of ZnO, TiO₂, and FA—Zn were found to be 0.016 min^-1, 0.017 min^-1, and 0.020 min^-1, respectively. There were two reasons for this: (1) FA—Zn was able to utilize both ultraviolet and visible parts of the solar spectrum, and (2) its Brunauere—Emmette—Teller surface area and porosity were significantly enhanced. This led to increased photon absorption and dye adsorption, thus exhibiting an energy-efficient performance. Therefore, FA—Zn, partly derived from waste, can serve as a suitable material for environmental remediation and practical solar energy applications.