Oxidation and isomerization of cyclohexane catalyzed by SO42-/Fe2O3-CoO under mild condition

SO(4)(2-)/Fe(2)O(3)-CoO solid catalyst was prepared and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transfer infrared (FT-IR) spectroscopy. Its catalytic activities in oxidation and isomerization of cyclohexane in air under mild condition were studied by UV, GC/MS and XPS. The results suggested that isomerization and oxidation of cyclohexane under mild conditions can synchronously performed and the catalytic activity of the catalyst can be improved by promotion of Co element into the sulfated iron. The high catalytic activities of catalysts may be related to the shift of the asymmetric stretching frequency of the SO bonds of sulfate species. Finally, the possible mechanism was also proposed.     

Importance of H(2)O(2)/Fe(2+) ratio in Fenton's treatment of a carpet dyeing wastewater

The effectiveness of the Fenton's reagent (H(2)O(2)/Fe(2+)) in the treatment of carpet dyeing wastewater was investigated under different operational conditions, namely, H(2)O(2) and FeSO(4) concentrations, initial pH and temperature. Up to 95% COD removal efficiency was attained using 5.5 g/l FeSO(4) and 385 g/l H(2)O(2) at a pH of 3, temperature of 50 degrees C. The H(2)O(2)/Fe(2+) ratio (g/g) was found to be between 95 and 290 for maximum COD removal. It was noteworthy that, keeping H(2)O(2)/Fe(2+) ratio constant within the range of 95-290, it became possible to decrease FeSO(4) concentration to 1.1 g/l and H(2)O(2) concentration to 96.3 g/l, still achieving nearly the same COD removal efficiency. The relative efficiencies of Fenton's oxidation and coagulation stages revealed that Fenton's coagulation removed organic compounds which were not removed by Fenton's oxidation, indicating that the Fenton's coagulation acted as a polishing step.     

Co3O4负载rGO/g-C3N4臭氧光催化降解2,4-二氯苯氧乙酸活性研究

通过简单的水热法制备了Co₃O₄/rGO/g-C₃N₄催化剂,并在可见光照射下用于光催化臭氧氧化降解2,4-二氯苯氧乙酸(2,4-D)。利用XRD, SEM, TEM, XPS, UV-vis DRS, FT-IR和瞬态光电流对样品进行测试表征。研究表明,Co₃O₄, rGO和g-C₃N₄形成异质结后光生电子-空穴(e^--h⁺)对的分离效率,e^-的迁移能力以及光催化臭氧氧化活性都明显提升。此外,0.5Co₃O₄/0.25rGO/GCN对2,4-D具有100%的去除率,并具有最高反应速率(k=0.070 9 min^-1)。经过计算得出光催化臭氧氧化2,4-D的协同因子为3.91,表明光催化和臭氧氧化间具有较好的协同效应。活性组分的捕获实验结果表明h⁺和·OH是光催...     

Decolourization of Methyl Orange using Fenton-like mesoporous Fe(2)O(3)-SiO(2) composite

Rapid decolourization of Methyl Orange by Fenton-like mesoporous Fe(2)O(3)-SiO(2) catalyst has been reported. The effect of various parameters such as initial pH, initial H(2)O(2) concentration, Fe content in the catalyst and initial dye concentration on decolourization process were studied. The results show that 20mg of mesoporous Fe(2)O(3)/SiO(2) composite (with Si/Fe=10) was sufficient to decolourize 0.6 mg/ml of Methyl Orange in presence of 2 ml of H(2)O(2) at an initial pH of 2.93 within 20 min. The pH range for effective decolourization (≥90%) was found to be 1-3. Leaching tests indicated that the activity of the catalyst was almost unaffected up to three consecutive cycles although ≤0.2 ppm of Fe ion was leached into treated water in each run.     

Preparation and characterization of Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film as electrode material for the degradation of phenol

In this work, a novel electrode of titanium substrate coated with mixed metal oxides of SnO(2), Sb(2)O(3), Nb(2)O(5) and PbO(2) was successfully prepared using thermal decomposition and electrodeposition. The surface morphology and the structure of the prepared thin film were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. Experimental results showed that the structure of the prepared electrode might be described as a Ti/SnO(2)-Sb(2)O(3)-Nb(2)O(5)/PbO(2) thin film and its surface was mainly comprised pyramidal-shape beta-PbO(2) crystals. The modified electrode had higher oxygen evolution potential than that of other PbO(2) modified electrodes. Electrocatalytic oxidation of phenol in aqueous solution was studied to evaluate the potential applications of this electrode in environmental science. The phenol removal efficiency in an artificial wastewater containing 0.50g/L phenol could reach 78.6% at 20 degrees C and pH 7.0 with an applied electricity density of 20mA/cm(2) and treatment time of 120min. When 21.3g/L chloride was added to this wastewater, the removal efficiency could reach to 97.2%.     

Ozonation of endocrine disrupting chemical BHA under the suppression effect by salt additive--with and without H(2)O(2)

The oxidation of fresh and saline wastewater containing an endocrine disrupting chemical (butylated hydroxyanisole, BHA) under different reaction conditions by ozonation and O(3)/H(2)O(2) was investigated at various pH levels. The observed pseudo-first-order reaction kinetics was justified through a combined direct ozone and indirect radical oxidation approach for the ozonation process. The BHA decay rates increased with the increase of the solution pH, but decreased as the NaCl concentration increased because of the consumption of ozone by chloride. A kinetic model was therefore derived for predicting BHA degradation at various initial pH levels and NaCl concentrations. For the O(3)/H(2)O(2) and O(3)/H(2)O(2)/Cl(-) processes, the rate of BHA removal was investigated at hydrogen peroxide concentration ranged from 0.5 to 5mM at pH 7. Different optimal H(2)O(2) dosages and decay rates were found for both processes due to the participation of reactions among O(3), H(2)O(2), OH* and Cl(-) as discussed in the paper.     

Efficient mineralization of dimethyl phthalate by catalytic ozonation using TiO2/Al2O3 catalyst

The removal of dimethyl phthalate (DMP), which is a pollutant of concern in water environments, was carried out by catalytic ozonation with TiO₂/Al₂O₃ catalysts. The heterogeneous catalytic ozonation was an ozonation process combined with the catalytic and adsorptive properties of the TiO₂/Al₂O₃ catalysts to significantly accelerate the mineralization efficiency. Semi-batch ozonation was performed under various experimental conditions including the fed ozone concentration, catalyst type, catalyst dosage, and ultraviolet radiation on the degradation of DMP. The complete removal of DMP was efficiently achieved by both sole and catalytic ozonation; meanwhile, the presence of the catalysts slightly accelerated the elimination rate of DMP. On the other hand, the mineralization efficiency, in terms of total organic carbon (TOC) removal, was substantially enhanced by employing the TiO₂/Al₂O₃ catalyst. The mineralization efficiency using the TiO₂/Al₂O₃ catalyst was the highest, followed in decreasing order by the Al₂O₃ catalyst, the TiO₂ catalyst, and sole ozonation. In addition, the use of the TiO₂/Al₂O₃ catalyst would increase the utilization efficiency of the fed ozone, especially in the late ozonation period. Furthermore, the decrease in the catalytic activity of the TiO₂/Al₂O₃ catalyst after multi-run experiments can be mostly recovered by an incineration process at a high temperature.     

Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole

Humic acid coated Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)/HA) were prepared for the removal of sulfathiazole from aqueous media. Fe(3)O(4)/HA exhibited high activity to produce hydroxyl (OH) radicals through catalytic decomposition of H(2)O(2). The degradation of sulfathiazole was strongly temperature-dependent and favored in acidic solution. The catalytic rate was increased with Fe(3)O(4)/HA dosage and H(2)O(2) concentration. When 3 g L(-1) of Fe(3)O(4)/HA and 0.39 M of H(2)O(2) were introduced to the aqueous solution, most sulfathiazole was degraded within 1h, and >90% of total organic carbon (TOC) were removed in the reaction period (6h). The major final products were identified as environmentally friendly ions or inorganic molecules (SO(4)(2-), CO(2), and N(2)). The corresponding degradation rate (k) of sulfathiazole and TOC was 0.034 and 0.0048 min(-1), respectively. However, when 3 g L(-1) of bare Fe(3)O(4) were used as catalyst, only 54% of TOC was eliminated, and SO(4)(2-) was not detected within 6h. The corresponding degradation rate for sulfathiazole and TOC was 0.01 and 0.0016 min(-1), respectively. The high catalytic ability of Fe(3)O(4)/HA may be caused by the electron transfer among the complexed Fe(II)-HA or Fe(III)-HA, leading to rapid regeneration of Fe(II) species and production of OH radicals.     

Photooxidative degradation of 4-nitrophenol (4-NP) in UV/H2O2 process: influence of operational parameters and reaction mechanism

The photooxidative degradation of 4-nitrophenol (4-NP) was studied in the UV/H2O2 process. The effects of applied H2O2 dose, initial 4-NP concentration and UV light intensity have been studied. Degradation was complete in 13 min and follows apparent first-order kinetics. The removal efficiency of 4-NP depends on the operational parameters and increases as the initial concentration of H2O2 and light intensity are increased but it decreases when the initial concentration of 4-NP is increased. From HPLC analysis, major intermediate products were hydroxyl derivatives of 4-NP as a result of photooxidative hydroxylation.     

羧甲基纤维素-Fe_3O_4复合纳米磁性材料的制备及其渗透性能

采用改进的氧化沉淀法在羧甲基纤维素(CMC)溶液中制备了以磁性纳米Fe3O4为核心,外包CMC的复合磁性纳米粒子。用透射电镜、X射线衍射、红外光谱、Zeta电位和震动样品磁强计对复合粒子进行了表面形貌、结构和磁学的表征。实验结果表明,CMC-Fe3O4复合纳米粒子为反尖晶石型,平均粒径约为40 nm;CMC在Fe3O4粒子表面是化学吸附;在相同pH值下,CMC-Fe3O4的表面Zeta电位低于纯相Fe3O4;CMC-Fe3O4的饱和磁化强度为36.74 emu.g-1;CMC-Fe3O4复合粒子在土壤介质中的过滤系数约为0.03 cm-1;在10 cm土柱渗透实验中,72%的CMC-Fe3O4复合粒子悬浊液穿过了土壤介质。     

非均相沉淀法制备纳米α-Al2O3/金属复合粉体

利用非均相沉淀法制备了平均粒径小于50 nm的α-Al₂O₃/W(Ni)复合粉体,并研究对比了纳米钨和镍对α-Al₂O₃相转变温度的影响。结果表明:纳米钨和镍的存在均可降低过渡型氧化铝向α型氧化铝转变的相变温度,但降低程度有所不同,含钨氧化铝于1000℃完成相变,而含镍氧化铝于1150℃完成相变;并且纳米第二相体积比越大,对相变温度的影响也越大。     

Simultaneous separation and speciation of inorganic As(III)/As(V) and Cr(III)/Cr(VI) in natural waters utilizing capillary microextraction on ordered mesoporous Al2O3 prior to their on-line determination by ICP-MS

In this paper, a system of flow injection (FI) capillary microextraction (CME) on line coupled with inductively plasma mass spectrometry (ICP-MS) was proposed for simultaneous separation and speciation of inorganic As(III)/As(V) and Cr(III)/Cr(VI) in natural waters. Ordered mesoporous Al2O3 coating was prepared by sol-gel technology and used as CME coating material. Various experimental parameters affecting the capillary microextraction of inorganic arsenic and chromium species have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.7 and 18 ng L(-1) for As(V) and Cr(VI), 3.4 and 74 ng L(-1) for As(III) and Cr(III), respectively, with an enrichment factor of 5 and a sampling frequency of 8h(-1). The relative standard deviations (R.S.D.) were 3.1, 4.0, 2.8 and 3.9% (C=1 ng mL(-1), n=7) for As(V), As(III), Cr(VI) and Cr(III), respectively. The proposed method was successfully applied for the analysis of inorganic arsenic and chromium species in mineral water, tap water and lake water with the recovery of 94-105%. In order to verify the accuracy of the method, two certified reference of GSBZ50027-94 and GSBZ50004-88 water samples were analyzed and the results obtained were in good agreement with the certified values. The ordered mesoporous Al2O3 coated capillary showed an excellent solvent and thermal stability and could be re-used for more than 30 times without decreasing extraction efficiency.     

Degradation of cyanobacteria toxin by advanced oxidation processes

Advanced oxidation processes (AOPs) using O(3), H(2)O(2), O(3)/H(2)O(2), O(3)/Fe(II), and Fenton treatment were investigated for the degradation of aqueous solutions of cyanobacteria. The effects of concentration of reactants, temperature, and pH on toxins degradation were monitored and the reaction kinetics was assessed. O(3) alone or combined with either H(2)O(2) or Fe(II) were efficient treatment for toxins elimination. A higher toxin oxidation tendency was observed with Fenton reaction; total toxins degradation (MC-LR and MC-RR) was achieved in only 60s. The ozonation treatment was successfully described by second-order kinetics model, with a first-order with respect to the concentration of either ozone or toxin. At 20 degrees C, with initial concentration of MC-LR of 1mg/L, the overall second-order reaction rate constant ranged from 6.79 x 10(4) to 3.49 x 10(3)M(-1)s(-1) as the solution pH increased from 2 to 11. The reaction kinetics of the other AOPs (O(3)/H(2)O(2), O(3)/Fe(II), and Fenton), were fitted to pseudo first-order kinetics. A rapid reaction was observed to took place at higher initial concentrations of O(3), H(2)O(2) and Fe(II), and higher temperatures. At pH 3, initial concentration of toxin of 1mg/L, the pseudo first-order rate constant, achieved by Fenton process, was in order of 8.76+/-0.7s(-1).     

Surface hydration states of commercial high purity α-Al2O3 powders evaluated by temperature programmed desorption mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy

The surface of three different grades of commercial high-purity α-Al₂O₃ powders produced by hydrolysis of aluminum alkoxide, which differ each other in SSA are evaluated by temperature programmed desorption mass spectrometry (TPDMS) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. For the DRIFT evaluation the powders were heated in situ under vacuum from 25 to 700 8C. The TPDMS spectra of desorbed H₂O were obtained by heating the samples under ultra high vacuum at a rate of 20 K min^K1 up to 1200 8C.

The presence of hydrogen bonded water molecules, amorphous Al(OH)₃ and AlOOH structures, as well as associated and isolated hydroxyl groups on the surface of all the a-Al₂O₃ powders investigated is demonstrated. On the surface of one of the powders the presence of crystalline Al(OH)₃ structures, as evidenced by an additional sharp peak in the H₂O TPDMS spectrum, is confirmed.     

Degradation of bisphenol A in aqueous solution by H2O2-assisted photoelectrocatalytic oxidation

A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.     

Photochemical degradation of diethyl phthalate with UV/H2O2

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.     

Interface structure and strain development during compression tests of Al2O3/Nb/Al2O3 sandwiches

The interface structure of an Al₂O₃/Nb/Al₂O₃ sandwich produced by solid-state diffusion bonding was investigated in detail by various transmission electron microscopy (TEM) methods. The joint possessed at one interface a , , and on the other interface a and orientation relationship. At both interfaces, misfit dislocations formed to compensate the lattice mismatch as found by high-resolution transmission electron microscopy (HRTEM). Electron energy-loss near edge structure (ELNES) studies revealed that the interface is terminating with an Al layer resulting in Al–Nb bonds. Identical sandwiches were investigated on the meso- and macroscopic scale by performing compression tests and simultaneously monitoring the strain development at (001)_Nb and crystal faces. The full-field optical strain measurements (FFOM) revealed that the strain is localized at the interfaces when observed at the (001)_Nb face while it is along the maximum shear directions of 36–54° inclined to the interface when observed at the face. The strain localization along a specific maximum shear direction results in the cleavage of Al₂O₃, always initiating from the interface possessing the and orientation relationship.     

TiO(2)/BaTiO(3)-assisted photocatalytic mineralization of diclofop-methyl on UV-light irradiation in the presence of oxidizing agents

Gas chromatograph-mass spectroscopic identification of intermediate products in the degradation of diclofop-methyl and the kinetics of the reaction has been investigated. Formation of 4-[(2,4-dichlorophenoxy) phenoxy] ethane and (2,4-dichlorophenoxy) phenol was investigated. The other intermediate products are 2,4-dichlorophenol, 2,4-dichlorobenzene, phenol and acetic acid have been ascertained. The decrease in the concentration of the parent/intermediate compounds is followed by UV-vis spectral study and the supportive information on the functional groups in the intermediates has been obtained from IR-spectroscopy. Degradation process proceeds with oxidation-reduction reaction by the attack of OH*, H*, O(2)*(-) free radicals, which are photogenerated on the UV-light illuminated TiO(2)/BaTiO(3) photocatalysts particles in aqueous medium. In this presentation another wide band gap semiconductor BaTiO(3) is shown to have comparable photocatalytic efficiency. The oxidizing agents are added to accelerate the rate of the reaction by enhancing the formation of free radicals. Based on the intermediates formed in the process of degradation, a suitable mechanism has been proposed.     

The mechanochemical reaction of C60 and Bi(NO3)3·5H2O

The mechanochemical reaction of C₆₀ and Bi(NO₃)₃·5H₂O was performed under ball-milling condition. The product was well characterized by spectroscopic methods such as IR, Raman, UV-vis, ¹³C NMR, as well as elemental analysis method. The spectroscopic investigation indicates that some hydroxyl and nitro groups are attached to the C₆₀ and no profound structural changes occur for the C₆₀ cage in the product. The elemental analysis gives an average composition of C₆₀(NO₂)₂(OH)₂₁ for the product. A possible mechanism is suggested for the reaction.     

Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III) two-stage oxidation process

A two-stage oxidation (UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III)) process was applied to mineralize bisphenol A (BPA) at pH(i) (initial pH) 7. We take advantage of the high oxidation potential of sulfate radicals and use persulfate as the 1st-stage oxidant to oxidize BPA to less complex compounds (stoichiometric ratio: [S(2)O(8)(2-)](0)/[BPA](0)=1). Afterwards, the traditional photo-Fenton process was used to mineralize those compounds to CO(2). To the best of our knowledge, this is the first attempt to utilize the two processes in conjunction for the complete degradation of BPA. During the 2nd-stage reaction, other oxidants (H(2)O(2) and Iron alone) were also employed to observe the extent of enhancement of photo-Fenton. Further, qualitative identification of both hydroxyl and sulfate radicals was performed to evaluate their dominance under different conditions. The BPA degradation in this UV/persulfate process formulated a pseudo-first-order kinetic model well, with a rate constant of approximately 0.038 min(-1) (25 degrees C), 0.057 min(-1) (35 degrees C), and 0.087 min(-1) (50 degrees C), respectively. The much lower activation energy (DeltaE = 26 kJ mol(-1)) was further calculated to clarify that the thermal-effect of an illuminated system differs from single heat-assisted systems described in other research. Final total organic carbon (TOC) removal levels of BPA by the use of such two-stage oxidation processes were 25-34%, 25%, and 87-91% for additional Fe(II,III) activation, H(2)O(2) promotion, and Fe(II,III)/H(2)O(2) promotions, respectively.