Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

微乳液法合成掺硫纳米TiO_2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚（Triton X-100）/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能。烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是提高,然后迅速降低;在600℃烧结2 h时催化剂的降解性能达到最佳。掺杂硫可提高TiO2的光催化活性,随着掺杂量的增加,催化剂对甲基橙的降解率先快速增加然后缓慢降低,当掺杂量为S/Ti（摩尔比）=0.01∶1时TiO2的光催化降解效果最好。催化剂在用量较小时迅速提高TiO2的光催化降解性能,而后随着用量的增大反而降低,当催化剂用量为1.5 g/L时,对甲基橙的降解效果最好。     

大尺寸大孔径TiO_2/SiO_2光催化剂的制备及甲醛去除研究

以大孔径SiO2为载体,通过钛酸丁酯溶液的浸渍、原位水解以及高温煅烧制备出大尺寸、大孔径的TiO2/SiO2光催化剂。利用自制空气净化装置对室内甲醛的清除进行研究,分别考察了TiO2的百分含量、紫外光光强、温度、湿度和空气流量等不同条件下TiO2/SiO2光催化剂对除去甲醛效率的影响。结果表明,反应温度从10～50℃依次升高,去除率逐渐下降。在相对湿度为50%,TiO2负载率为55.6%,流量为8 m3/h时,甲醛的最佳除去率达96.5%;经过7周时间的考察,发现TiO2/SiO2光催化剂的催化活性没有明显的下降。     

Novel imazethapyr detoxification applying advanced oxidation processes

Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O?), and hydrogen peroxide tied to UV-irradiation (H?O?/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O?/UV), ozonation joined to titanium dioxide photo-catalysis (TiO?/UV+O?), sole photo-catalysis (TiO?/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO?/UV+H?O?) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

Photocatalytic degradation of an organophosphorus pesticide phosalone in aqueous suspensions of titanium dioxide

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO2 particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. The half-life (DT50) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K=0.0532 min(-1)). The half-life time of photomineralization in the concentration range of 7.5-20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

Degradation of azo dye Procion Red MX-5B by photocatalytic oxidation

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2O2, the highest reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2O2, the reaction was the fastest at initial pH of 3-5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW/cm2, were determined to be: TiO2 concentration, 500 mg/l; initial H2O2 concentration, 10 mM; initial pH, 5.0. Monitoring of TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was (were) resistant to PCO might have accumulated.     

Photocatalytic degradation of the herbicide pendimethalin using nanoparticles of BaTiO3/TiO2 prepared by gel to crystalline conversion method: a kinetic approach

Photocatalytic degradation of the herbicide, pendimethalin (PM) was investigated with BaTiO3/TiO2 UV light system in the presence of peroxide and persulphate species in aqueous medium. The nanoparticles of BaTiO3 and TiO2 were obtained by gel to crystallite conversion method. These photo catalysts are characterized by energy dispersive x-ray analysis (EDX), scanning electron microscope (SEM), x-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) adsorption isotherm and reflectance spectral studies. The quantum yields for TiO2 and BaTiO3 for the degradation reactions are 3.166 Einstein m(-2) s(-1) and 2.729 Einstein m(-2) s(-1) and catalytic efficiencies are 6.0444 x 10(-7) mg(-2)h(-1)L2 and 5.403 x 10(-7) mg(-2)h(-1)L2, respectively as calculated from experimental results. BaTiO3 exhibited comparable photocatalytic efficiency in the degradation of pendimethalin as the most widely used TiO2 photocatalyst. The persulphate played an important role in enhancing the rate of degradation of pendimethalin when compared to hydrogen peroxide. The degradation process of pendimethalin followed the first-order kinetics and it is in agreement with Langmuir-Hinshelwood model of surface mechanism. The reason for high stability of pendimethalin for UV-degradation even in the presence of catalyst and oxidizing agents were explored. The higher rate of degradation was observed in alkaline medium at pH 11. The degradation process was monitored by spectroscopic techniques such as ultra violet-visible (UV-Vis), infrared (IR) and gas chromatography mass spectroscopy (GC-MS). The major intermediate products identified were: N-propyl-2-nitro-6-amino-3, 4-xylidine, (2, 3-dimethyl-5-nitro-6-hydroxy amine) phenol and N-Propyl-3, 4-dimethyl-2, 6-dinitroaniline by GC-MS analysis and the probable reaction mechanism has been proposed based on these products.     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

水体中酮硝基麝香的臭氧氧化降解研究

采用臭氧氧化水体中的酮硝基麝香,考察pH、H2O2等因素对降解程度的影响,结果表明提高初始pH能加快酮硝基麝香的氧化降解,当pH为12时,反应时间1 h,酮硝基麝香几乎完全去除,浓度为2 mol/L和5 mol/L的H2O2存在有利于O3分解生成·OH自由基,使得酮硝基麝香的氧化降解速率加快,当H2O2浓度超过5 mol/L,H2O2会成为·OH的清除剂,降低·OH利用率;无论O3单独作用和O3/H2O2协同作用,酮硝基麝香降解符合准一级动力学规律;酮硝基麝香氧化降解产物包括甲酸、二乙酸和硝酸根等,其中硝基从苯环上脱落降低了硝基麝香对环境的风险.     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.     

CuO/γ-Al_2O_3类Fenton试剂降解丁基黄药

CuO/γ-Al2O3类Fenton试剂是降解丁基黄药的优良试剂。该试剂与传统的Fenton试剂相比,提高了反应的pH值,可在较高pH（4~5）条件下反应,而传统的Fenton试剂的适宜pH值一般在3以下。采用单因素实验和正交实验相结合的方法研究了pH、催化剂投加量、过氧化氢投加量以及反应时间对丁基黄药降解效果的影响,并对催化剂的使用寿命进行了探讨。研究结果表明,反应的最佳条件为：pH为4~5,催化剂投加量为6 g/L,过氧化氢用量为30 mg/L,反应30min。在此反应条件下,丁基黄药的降解率达98%以上;影响丁基黄药降解效果的因素大小顺序为：pH〉反应时间〉H2O2用量〉催化剂投加量,其中pH对CuO/γ-Al2O3类Fenton试剂降解丁基黄药的影响最为显著。     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

Hydrogen peroxide mediated photodegradation of phenol as studied by a flash photolysis/HPLC technique

The technique of flash photolysis followed by high-performance liquid chromatography has been applied to the study of the photodegradation of phenol (I) in the presence of hydrogen peroxide. Progress of the reaction of I (0.1 mM) in undegassed aqueous solution ([H2O2]/[I] = 200/l) was observed by using multiple flashes (16 J). Analysis after a single flash indicated that catechol and hydroquinone were the primary products of the reaction. The reaction was found to be independent of pH in the range 7.0-9.0, but the yield of degradation decreased at pH > 9.0 and at pH < 7.0. The effects of the hydrogen peroxide concentration and flash energy on the chemical yield of the pollutant degradation, and product formation, were investigated as well. The mechanism of the reaction is discussed. A possibility of the application of flashlamps as powerful sources of the UV irradiation in industrial reactors for wastewater treatment is suggested.     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。