Morphologies of zinc oxide particles and their effects on photocatalysis

ZnO powders with different morphologies were synthesized by alkali precipitation, organo-zinc hydrolysis, and spray pyrolysis. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these ZnO powders. We investigated the relationship between photocatalytic activity and crystallinity, surface area, or morphology. Results indicate that the photocatalytic activity of ZnO powder depends on crystallinity rather than surface area for the same original ZnO powders prepared by equal conditions other than the difference in calcination temperature. However, no direct relationship between photocatalytic activity and crystallinity or surface area was found for the differently original ZnO powders prepared by different methods, or the same method with different conditions. Instead, we find that the particle morphology significantly affects its photocatalysis.     

Advanced oxidation of a pulp mill bleaching wastewater.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.     

ZnO/LixNi1-xO光催化降解甲基橙的研究

采用溶胶凝胶法制备LixNi1-xO和ZnO粉体,利用球磨法制备ZnO/LixNi1-xO复合粉体,以紫外光为光源,通过降解甲基橙,研究了锂掺杂及n-p复合对氧化镍的光催化性能影响。结果表明：当投放量为0.1 g/L,x≤0.075（摩尔分数）的锂掺杂氧化镍均比未掺杂氧化镍的光催化活性高。当锂掺杂摩尔分数为0.025,投放量为0.4 g/L时锂掺杂氧化镍的光催化活性最佳,甲基橙最高降解率达到93.1%。当ZnO/Li0.025Ni0.975O在质量比为1∶1,投放量为0.2 g/L时光催化活性最佳,甲基橙最高降解率达到98.1%。     

Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.     

Application of activated M/ZnO (M = Mn,Co, Ni,Cu, Ag) in photocatalytic degradation of diazo textile coloring dye

Activated ZnO powder has been prepared by procedures involving first its dissolution in nitric acid, then simultaneous treatment by adding NH₄OH and CO₂ bubbling leading to precipitation as Zn(OH)CO₃ (ZH) and further thermal decomposition of ZH at 400 °C. The gas evolution leads to formation of pores and increase in the specific surface area. Chemically activated M/ZnO powders doped with Mn, Co, Ni, Cu, and Ag have been obtained by the impregnation method. The samples have been characterized by ultraviolet-visible (UV-Vis) spectroscopy, diffuse reflectance (DR) UV-Vis, X-ray diffraction (XRD), single point Brunauer–Emmet–Teller (BET), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) methods. The experiments have shown that metal-doped activated ZnO powders possess higher photocatalytic activities in oxidative discoloration of model contaminant textile coloring dye Reactive Black 5 in slurry reactor compared to that of the pure ZnO. The XRD and XPS data have shown the presence of defects, nonstoichiometricity implying the formation of solid solutions. Copper-doped (1.5 wt%) activated ZnO (Cu²⁺ replaces Zn²⁺) is outstanding in its photocatalytic performance in discoloration of the dye due to the higher specific surface area and improved charge carrier separation.     

新型可见光催化剂BiVO4降解中成药制药废水

以Bi(NO3)3.5H2O和NH4VO3为原料,采用水热法制备了新型可见光BiVO4催化剂,并用X-射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(IR)和紫外-可见光漫反射光谱(UV-vis DRS)对产品进行了结构表征,并将其应用于光催化降解中成药制药废水降解反应中,通过正交实验和单因素分析,考察了催化剂用量、空气流量、溶液pH值和助氧化剂H2O2对制药废水COD去除率、脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.41 eV,并具有良好的可见光催化活性。对于经10倍稀释的制药废水,BiVO4添加量为2 g/L,通氧量为120 L/h,助氧化剂H2O2添加量为1 mL,不改变废水pH值,在400 W金属卤化物灯离液面11 cm照射反应180 min的条件下,制药废水的COD去除率为94.3%,脱色率为95.6%,得到了较好的降解。     

Photocatalytic degradation of Orange G dye under solar light using nanocrystalline semiconductor metal oxide

Introduction

The photocatalytic degradation of Orange G (OG) dye has been investigated using synthesised nanocrystalline ZnO as a photocatalyst and sunlight as the irradiation source. The formation of ZnO prepared from its precursor was confirmed through FT-IR and powder X-ray diffraction analyses.

Materials and methods

Surface morphology was characterised by scanning electron microscope and transmission electron microscope analysis. Band gap energy of synthesised nanocrystalline ZnO was calculated using diffuse reflectance spectroscopy (DRS). Different experimental parameters such as effects of pH, dye concentrations and mass of catalyst were standardised in order to achieve complete degradation of the dye molecules under solar light irradiation.

Results

The kinetics of oxidation of OG was also studied. The complete degradation of OG was evident after 90 min of irradiation at an initial pH of 6.86. The degradation of OG was confirmed by UV?CVisible spectrophotometer, high-pressure liquid chromatography, ESI-Mass and chemical oxygen demand analyses.

Conclusion

The adsorption of dye onto catalytic surface was analysed employing model equations such as Langmuir and Freundlich isotherms, and it was found that the Langmuir isotherm model best fitted the adsorption data. The solar photodegradation of OG followed pseudo-first-order kinetics. HPLC and ESI-Mass analyses of the degraded samples suggested that the dye molecules were readily degraded under solar irradiation with nanocrystalline ZnO.     

UV/ozone degradation of gaseous hexamethyldisilazane (HMDS)

As a carcinogen, hexamethyldisilazane (HMDS) is extensively adopted in life science microscopy, materials science and nanotechnology. However, no appropriate technology has been devised for treating HMDS in gas streams. This investigation evaluated the feasibility and effectiveness of the UV (185+254nm) and UV (254nm)/O(3) processes for degradation of gaseous HMDS. Tests were performed in two batch reactors with initial HMDS concentrations of 32-41mgm(-3) under various initial ozone dosages (O(3) (mg)/HMDS (mg)=1-5), atmospheres (N(2), O(2), and air), temperatures (28, 46, 65 and 80 degrees C), relative humilities (20%, 50%, 65%, 99%) and volumetric UV power inputs (0.87, 1.74, 4.07 and 8.16Wl(-1)) to assess their effects on the HMDS degradation rate. Results indicate that for all conditions, the decomposition rates for the UV (185+254nm) irradiation exceeded those for the UV (254nm)/O(3) process. UV (185+254nm) decompositions of HMDS displayed an apparent first-order kinetics. A process with irradiation of UV (185+254nm) to HMDS in air saturated with water at temperatures of 46-80 degrees C favors the HMDS degradation. With the condition as above and a P/V of around 8Wl(-1), k was approximately 0.20s(-1) and a reaction time of just 12s was required to degrade over 90% of the initial HMDS. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254nm) were found to be caused by OH free-radical oxidation produced from photolysis of water or O((1)D) produced from photolysis of oxygen. The economic evaluation factors of UV (185+254nm) and UV (254nm)/O(3) processes at different UV power inputs were also estimated.     

新型可见光催化剂BiVO4降解中成药制药废水

以Bi（NO3）3.5H2O和NH4VO3为原料,采用水热法制备了新型可见光BiVO4催化剂,并用X-射线衍射（XRD）、扫描电子显微镜（SEM）、红外光谱（IR）和紫外-可见光漫反射光谱（UV-vis DRS）对产品进行了结构表征,并将其应用于光催化降解中成药制药废水降解反应中,通过正交实验和单因素分析,考察了催化剂用量、空气流量、溶液pH值和助氧化剂H2O2对制药废水COD去除率、脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.41 eV,并具有良好的可见光催化活性。对于经10倍稀释的制药废水,BiVO4添加量为2 g/L,通氧量为120 L/h,助氧化剂H2O2添加量为1 mL,不改变废水pH值,在400 W金属卤化物灯离液面11 cm照射反应180 min的条件下,制药废水的COD去除率为94.3%,脱色率为95.6%,得到了较好的降解。     

Measurement of the pesticide methomyl by modified quartz crystal nanobalance with molecularly imprinted polymer

A simple and cost-effective analysis method based on quartz crystal nanobalance (QCN) coated with a molecularly imprinted polymer (MIP) for measurement of methomyl was investigated. In the first part of this study, a sensitive, selective and reliable quartz crystal nanobalance (QCN) sensor was designed for the selective determination of methomyl in aqueous solutions. In the second part, in order to demonstrate the applicability and performance of the fabricated sensor in the real world situation, it was successfully applied for the determination of methomyl residual in photo catalytic degradation by ZnO powders in aqueous solutions. The fabricated sensor presents a high selectivity and sensitivity (4.56 Hz per mg L^?1) for methomyl and it can be used for determination of methomyl concentration ranged between 1 to 45 mg L^?1. Furthermore, good reproducibility, R.S.D. = 2.14% (n = 5) was observed. To investigate the performance of the sensor, the change in the insecticide concentration during the photocatalytic degradation of methomyl by ZnO was investigated by QCN and UV/Vis spectroscopy. Results obtained from QCN sensor and UV/Vis spectroscopy measurement are in good mutual agreement. So the fabricated sensor may provide an efficient, low cost, easy-to-use method for the in-field evaluation of specific targeted analytes in aqueous solutions which in turn may lead to improved food and water safety.     

Ag/ZnO hollow sphere composites: reusable photocatalyst for photocatalytic degradation of 17α-ethinylestradiol

Characterizations of Ag/ZnO hollow sphere by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectra, and UV–vis absorption spectra have been made after its synthesis. The results showed that the composite was hollow structure with diameters of about 1–4 μm. The samples synthesized were tested and identified as silver doped ZnO, which have extended and boosted the spectral absorption. The photocatalytic activity of Ag/ZnO hollow spheres was assessed using 17α-ethinylestradiol aqueous solution under UV irradiation. It has been observed that the 17α-ethinylestradiol absorption efficiency and degradation rate is higher for Ag/ZnO hollow spheres. As reusable photocatalysts, Ag/ZnO hollow spheres which could be easily separated from a suspension will facilitate their application in wastewater treatment with enhanced photostability.     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

Toxicity of nanosized and bulk ZnO, CuO and TiO2 to bacteria Vibrio fischeri and crustaceans Daphnia magna and Thamnocephalus platyurus

As the production of nanoparticles of ZnO, TiO2 and CuO is increasing, their (eco)toxicity to bacteria Vibrio fischeri and crustaceans Daphnia magna and Thamnocephalus platyurus was studied with a special emphasis on product formulations (nano or bulk oxides) and solubilization of particles. Our innovative approach based on the combination of traditional ecotoxicology methods and metal-specific recombinant biosensors allowed to clearly differentiate the toxic effects of metal oxides per se and solubilized metal ions. Suspensions of nano and bulk TiO2 were not toxic even at 20 g l(-1). All Zn formulations were very toxic: L(E)C50 (mg l(-1)) for bulk ZnO, nanoZnO and ZnSO4.7H2O: 1.8, 1.9, 1.1 (V. fischeri); 8.8, 3.2, 6.1 (D. magna) and 0.24, 0.18, 0.98 (T. platyurus), respectively. The toxicity was due to solubilized Zn ions as proved with recombinant Zn-sensor bacteria. Differently from Zn compounds, Cu compounds had different toxicities: L(E)C50 (mg l(-1)) for bulk CuO, nano CuO and CuSO4: 3811, 79, 1.6 (V. fischeri), 165, 3.2, 0,17 (D. magna) and 95, 2.1, 0.11 (T. platyurus), respectively. Cu-sensor bacteria showed that toxicity to V. fischeri and T. platyurus was largely explained by soluble Cu ions. However, for Daphnia magna, nano and bulk CuO proved less bioavailable than for bacterial Cu-sensor. This is the first evaluation of ZnO, CuO and TiO2 toxicity to V. fischeri and T. platyurus. For nano ZnO and nano CuO this is also a first study for D. magna.     

Remediation of PCB contaminated soils using iron nano-particles

In this study, iron nano-particles were used to remediate PCB contaminated soil and an attempt was made to maximize PCB destruction in each treatment step. The results show that nano-particles do aid in the dechlorination process and high PCB destruction efficiencies can be achieved. The destruction efficiency during the preliminary treatment (mixing of soil and iron nano-particles in water) can be increased by increasing the water temperature. The maximum thermal destruction (pyrolysis/combustion of soil after preliminary treatment) of soil-bound PCBs occurs at 300 degrees C in air. A minimum total PCB destruction efficiency of 95% can be achieved by this process. The effect of changing treatment parameters such as type of mixing, time of mixing and mixing conditions and application of other catalysts like iron oxide and V(2)O(5)/TiO(2) was also investigated. It was found that at 300 degrees C in air, iron oxide and V(2)O(5)/TiO(2) are also good catalysts for remediating PCB contaminated soils.     

负载型TiO2固定相光催化降解含酚废水的试验研究

以20W紫外灯为光源,研究了将TiO2粉末负载在硅胶颗粒上,对含酚废水进行光催化降解.由试验得出光催化反应过程中的工艺条件,在此基础上添加H2O2、Fe3+、Cu2+,反应1 h后,苯酚的降解率达95%以上.     

纳米ZnO/PS薄膜的制备及光降解性能

利用纳米ZnO与聚苯乙烯(PS)高速共混法制备了一种在紫外光下具有自降解性能的复合薄膜.分析表明,经过KH570处理的纳米ZnO与PS通过化学键的方式桥联在一起.TG分析表明,复合薄膜的耐热性较PS有所提高;SEM图像显示0.5 wt％ ZnO在PS薄膜表面分布均匀,经过UV照射后薄膜表面出现光腐蚀现象.复合薄膜紫外光自降解实验表明:0.5 wt％ ZnO/PS薄膜在15W的紫外灯照射下,15d的自降解率为3.715％.     

Reutilization of granite powder as an amendment and fertilizer for acid soils

The properties of granite powders--a granite manufacturing waste product-were analyzed to assess their potential use as amendments and fertilizers on acid soils. Two types of powders were characterized: one produced during cutting of granite with a diamond-edged disc saw, comprising only rock powder, the other produced during cutting with a multi-blade bandsaw, containing calcium hydroxide and metal filings added during the cutting procedure. The acid neutralizing capacity of the granite powders was assessed in short- (2-3 h) and medium-term (1-30 d) experiments. The powders showed a buffering capacity at around pH 8, which corresponded to the rapid dissolution of basic cations, and another buffering effect at pH<4.5, attributable to the dissolution of Fe and Al. The acid neutralizing capacity (ANC) determined in the short-term experiments, to a final pH of 4.5, varied between 5 and 61 cmol H+kg(-1) powder. The ANC to pH 4.5 obtained in the medium-term experiments was much higher than that obtained in the short-term experiments, reaching a maximum ANC value of 200 cmol H+kg(-1) powder. There was no great difference in the neutralizing capacity determined at between 1 and 30 d. The most abundant elements in acid solutions obtained at the end of medium-term experiments were Mg and Ca for disc saw powders, whereas Ca and Fe (at pH<5) were the most soluble elements in the bandsaw powders. The rapid release of these cations suggests the possible effective use of the granite powders as a source of nutrients on being added to acid soils.     

Effects of freezing on the survival of Escherichia coli and Bacillus and response to UV and chlorine after freezing.

Escherichia coli (E. coli) and Bacillus megaterium bacteria were frozen at -15 degrees C using a freezer and a spray freezing method. The frozen Bacillus spores were also exposed to UV and free chlorine. An average of 4.7-log inactivation was obtained from the spray ice with 2-day storage time, while the freezer freezing only caused 0.84-log reduction with the same storage time. Significantly higher inactivation levels were observed for the E. coli cells with 2-day storage compared with those without storage. The spray freezing was found more effective in killing the E. coli cells, while more cells were sublethally injured by the freezer freezing. Freezing did not kill the Bacillus megaterium spores, but affected their response to UV and chlorine. Greater inactivation levels were observed at higher free chlorine doses or longer contact time, and the UV fluence-response curve showed initial rapid kill followed by tailing for the frozen spores.     

Formulation factors that can reduce the formation of the phytotoxic impurity, N,N'-dibutylurea, from benomyl

Fungicide benomyl is easily decomposed to carbendazim (MBC) and butyl isocyanate (BIC) in formulation, BIC is further hydrolyzed to butylamine. The BIC also reacts with butylamine to form N,N'-dibutylurea (DBU), a phytotoxic compound. The purpose of this study was to investigate the effects of selected additives and the manufacturing method of benomyl water dispersible granules (WG) on reducing DBU content in benomyl formulations. The manufacturing methods studied were granulation by extrusion, fluid bed spray, and spray dry. For the extrusion method, each benomyl powder formulation was homogenized by kneading with 20% v/w of 95% ethanol instead of water. After granulation, the percentages of the active ingredient benomyl and its degradation product carbendazim in each formulation were determined. For the fluid bed spray method, two formulations of wettable powders were formed. The first sample was granulated using 5% Na(2)SO(4) as the binder solution; the second sample used 2% urea. Changes in the active ingredient content after granulation were determined for each sample. For the spray dry method, four basic formulations of 70% benomyl, 5% sodium dodecyl sulfate (SDS) and 10% or 20% sodium sulfate were prepared, to study the effects of HMTA, urea and dispersant on reducing DBU formation in formulation. The DBU content of each formulation was measured for the fresh samples and after 1 year of storage. The results showed that urea had a stabilizing effect on benomyl, and reduced DBU formation. BIC increased benomyl yield during manufacturing, which reduced DBU content in fresh samples but allowed a greater potential for future DBU formation since it did not stabilize the extra benomyl. HMTA was found to reduce DBU in both aqueous BIC and prepared formulations. The study discusses how each of the selected constituents affected DBU formation and how commercial formulations can be improved to reduce DBU formation. From this study, it is clear that a safer benomyl formulation can be developed.     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).