Activated persulfate by DBD plasma and activated carbon for the degradation of acid orange Ⅱ

In this study, the effect of activated peroxydisulfate(PDS) by dielectric barrier discharge(DBD) plasma and activated carbon(HGAC) on the removal of acid orange Ⅱ(AOⅡ) was investigated. The effects of applied voltage, PDS dosage, HGAC dosage, initial pH value, and inorganic anions on the removal rate of AOⅡ were discussed. The main free radicals degrading azo dyes during the experiment were also studied. Experimental results show that the removal rate of AOⅡ in DBD/HGAC/PDS synergistic system is much higher than that in the single system. With the applied voltage of 16 kV, HGAC dosage of 1 g l-1, PDS and AOⅡ molar ratio of 200:1, initial pH value of 5.4 and concentration of AOⅡ solution of 20 mg l-1, the removal rate of AOⅡ reached 97.6% in DBD/HGAC/PDS process after 28 min of reaction.Acidic and neutral conditions are beneficial for AOⅡ removal. Sulfate and hydroxyl radicals play an important role in the removal of AOⅡ. Inorganic anions are not conducive to the removal of AOⅡ.

含铁柱撑膨润土光催化降解Orange Ⅱ

制备了两种含铁柱撑膨润土(FeAlBent和FeBent),用XRD、BET、TEM对它们进行了性能表征。以偶氮染料OrangeⅡ为目标降解物,考察了它们作为复相Fenton催化剂的光催化性能,以及溶液的pH、H2O2浓度、催化剂用量对OrangeⅡ降解的影响,并与相应的均相Fenton反应进行了比较。结果表明FeAlBent和FeBent具有很高的比表面积(分别为194.2和114.6m2/g),用FeAlBent或FeBent作光催化剂的复相光助Fenton反应的催化性能明显优于相应的均相光助Fenton反应。此外复合铁铝柱撑膨润土(FeAlBent)比单一的铁柱撑膨润土(FeBent)在反应过程中具有更低的铁离子溶出量,它们还具有分离简单、重复使用性好等特点。

Degradation of Acid Orange Ⅱ Using Negative Pulsed Discharge Plasma from a Nozzle-cylinder Electrode Coated with TiO2

Many sub-products of pulsed discharge,such as ultraviolet light,strong electric fields,shock waves and active species,are effective in treating wastewater.To improve the efficiency of the discharge plasma technology in removing pollutants,adding TiO2 photo-catalyst to pulsed discharges could help.A negative-pulsed-discharge system,which has nozzle discharge electrodes with or without TiO2 coating,is used to degrade azo dye Acid Orange Ⅱ,and the effects of several key conditions(maximum pulse voltage,pulse repetition frequency,initial mass concentration of Acid Orange Ⅱ initial solution pH,treatment duration,the phase of discharge,and the existence of TiO2) on the degradation are experimentally investigated.The degradation of Acid Orange Ⅱ increases with maximum pulse voltage,pulse repetition frequency,and treatment duration,and it is larger when putting the discharge electrode on the solution surface than in air or inside the solution,i.e.the discharge in gas phase is more effective than that in gas-liquid phase or liquid phase.The degradation decreases as the initial mass concentration of the solution increases.It also relates to pH and is higher at acidic conditions than at neutral or alkaline conditions.Compared to treatments without TiO2,the ones using the nozzle discharge electrode with TiO2 coated increase the degradation of Acid Orange Ⅱ by 5 %.It is concluded that the proposed system with TiO2 added in can remove Acid Orange Ⅱ from wastewater effectively.

Formation of the Inclusion Complex of Orange Ⅱ with β-Cyclodextrin and Its Photostability

Inclusion complex of Orange II with β-Cyclodextrin (β-CD) and the anti-photolysis effect under UV-light were investigated. The molar ratio of inclusion complex of β-Cyclodextrin and Orange Ⅱ is 1∶1. The formation constant K=1.236×10 3 L/mol was determined by the UV and Fluorescence spectra respectively, which was quite in accordance with the calculation with a modified Benesi-Hildbrand equation. The inclusion complex was characterized by the IR spectra and the molar ratio of inclusion complex is 1∶1 too. The formation constant K=1.266×10 3 L/mol was determined by 1 H NMR analysis and was nearly the same by UV and fluorescence spectra. The photocatalytic decolorization rate of Orange Ⅱ solutions containing β-CD and TiO_ 2 was smaller by 51.9% than that of the Orange Ⅱ solutions only containing TiO_ 2 , while in the case of direct photolysis of Orange Ⅱ solutions, β-CD can lower the photolysis rate by 48.1% under UV-light. This result indicates β-CD can inhibit the photolysis and photocatalytic decolorization of Orange Ⅱ under UV-light. The β-CD inclusion complex was found to be persistent to UV-light photolysis.

Photocatalytic Degradation of Organic Dye Methyl Orange with Phosphotungstic Acid

Silicotungstic acid and phosphotungstic acid were prepared and characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the prepared catalysts possess classical Keggin structure. The factors on the degradation of methyl orange, such as the kind of catalyst, the amount of catalyst, the original concentration of dye and illumination time were investigated under metal halide lamp. The degradation of methyl orange is up to 93.6% with phosphotungstic acid at the best reaction conditions at 8.89 g/L concentration of phosphotungstic acid, 5.56 mg/L concentration of methyl orange and 80 min illumination time.

Regeneration of Acid Orange 7 Exhausted Granular Activated Carbon Using Pulsed Discharge Plasmas

In this paper, a pulsed discharge plasma （PDP） system with a multi-needle-to-plate electrodes geometry was set up to investigate the regeneration of acid orange 7 （AO7） exhausted granular activated carbon （GAC）. Regeneration of GAC was studied under different conditions of peak pulse discharge voltage and water pH, as well as the modification effect of GAC by the pulse discharge process, to figure out the regeneration efficiency and the change of the GAC structure by the PDP treatment. The obtained results showed that there was an appropriate peak pulse voltage and an optimal initial pH value of the solution for GAC regeneration. Analyses of scanning electron microscope （SEM）, Boehm titration, Brunauer-Emmett-Teller （BET）, Horvath-Kawazoe （HK）, and X-ray Diffraction （XRD） showed that there were more mesopore and macropore in the regenerated GAC and the structure turned smoother with the increase of discharge voltage; the amount of acidic functional groups on the GAC surface increased while the amount of basic functional groups decreased after the regeneration process. From the result of the XRD analysis, there were no new substances produced on the GAC after PDP treatment.

Understanding changes in volatile compounds and fatty acids of Jincheng orange peel oil at different growth stages using GC-MS

Jincheng orange(Citrus sinensis Osbeck)is widely grown in Chongqing,China,and is commonly consumed because of its characteristic aroma contributed by the presence of diverse volatile compounds.The changes in aroma during the development and maturation of fruit are indicators for ripening and harvest time.However,the influence of growth stages on the volatile compounds in Jincheng orange remains unclear.In addition,volatiles originate from fatty acids,most of which are the precursors of volatile substances.On this basis,gas chromatography-mass spectrometry(GC-MS)was performed to elaborate the changes in volatile constituents and fatty acids as precursors.This study tested proximately 60 volatiles and 8 fatty acids at 9 growth and development stages(AF1-AF9).Of those compounds,more than 92.00%of total volatiles and 87.50%of fatty acids were terpenoid and saturated fatty acids,respectively.As shown in the PCA plot,the AF5,AF6,and AF9 stages were confirmed as completely segregated and appeared different.In addition,most of the volatiles and fatty acids first increased at the beginning of the development stage,then decreased from the AF6 development stage,and finally increased at the AF9 maturity stage.Moreover,the highest contents of terpenoid,alcohols,aldehydes,ketones,and saturated fatty acids in Jincheng orange peel oil were d-limonene,linalool,octanal,cyclohexanone,and stearic acid during development stages,respectively.Our results found that the growth stages significantly affected the volatile constituents and precursors in Jincheng orange peel oil.

Synthesis of the Prospective Anticancer Molecule Perillic Acid from Orange Essential Oil by the Yeast <i>Yarrowia lipolytica</i>

The bioconversion of the hydrophobic and volatile limonene to perillic acid, a potential anticancer agent, by the yeast Yarrowia lipolytica was studied in two steps. Firstly, experimental design was used for process optimization using high-purity limonene as substrate and secondly orange essential oil containing 89.1% limonene was used as substrate under the previously optimized conditions. Limonene concentration and pH were identified by fractional factorial design as significant factors and were optimized by central composite design. Under optimized process conditions (0.16% (v/v) limonene;pH 6.9), the 24 h biotransformation process resulted in the accumulation of 0.368 g·L-1 of perillic acid corresponding to a molar yield of 23.1%. A subsequent substrate addition under the same reaction conditions doubled perillic acid concentration to 0.793 g·L-1 and a molar yield of 24.2%. The use of orange essential oil under the optimized reaction conditions increased both perillic acid accumulation and yield to 0.872 g·L-1 and 29.7%, respectively. The robustness of Y. lipolytica allowed the efficient biotransformation of a crude by-product of the citrus industry into a valuable fine chemical.

Adsorption of acid orange 7 from aqueous solutions by bottom ash

Bottom ash. a power plant waste, was used to adsorb acid orange 7. The adsorption of acid orange 7 in aqueous solutions onto bottom ash was studied as functions of particle size. dosage, initial concentration and agitation time by batch experiments. Under conditions of bottom ash dosage of 1.5 g/50 ml and 5 g/50 ml for 〈0.074 mm and 0.074 mm-0.2 mm of bottom ash, respectively, it could achieve 99.1% and 87.6% dye removal efficiency. The adsorption isotherms for the bottom ash could be well described by both Freundlich and Langmuir isotherms. The calculated dye adsorption capacities of bottom ash for the particle size of 0.074 mm -0.2 mm and 〈0.074 mm were 2.78 mg/g and 10.21 mg/g, respectively. The results indicated that the dye uptake process fitted to the pseudo-first-order kinetic model better than the pseudo-second-order. The data were also fitted to intraparticle diffusion model by two adsorption stages, due to the difference in rate of mass transfer in the initial and final stages of adsorption. Significant variations were observed in the FTIR spectra and Stem photographs of bottom ash after adsorption. The column parameters were calculated by breakthrough curves at different flow rates and bed depths.

Photo-induced transformations of Hg(Ⅱ) species in the presence of Nitzschia hantzschiana,ferric ion,and humic acid

Effects of algae Nitzschia hantzschiana, Fe（Ⅲ） ions, humic acid, and pH on the photochemical reduction of Hg（Ⅱ） using the irradiation of metal halide lamps （λ〉 365 nm, 250 W） were investigated. The photoreduction rate of Hg（Ⅱ） was found to increase with increasing concentrations of algae, Fe（Ⅲ） ions, and humic acid. Alteration of pH value affected the photoreduction of Hg（Ⅱ） in aqueous solution with or without algae. The photoreduction rate of Hg（Ⅱ） decreased with increasing initial Hg（Ⅱ） concentration in aqueous solution in the presence of algae. The photochemical kinetics of initial Hg（Ⅱ） and algae concentrations on the photoreduction of Hg（Ⅱ） were studied at pH 7.0. The study on the total Hg mass balance in terms of photochemical process revealed that more than 42% of Hg（Ⅱ） from the algal suspension was reduced to volatile metallic Hg under the conditions investigated.

Adsorption of Cu(Ⅱ) on humic acids derived from different organic materials

The adsorption of Cu（Ⅱ） from aqueous solution onto humic acid （HA） which was isolated from cattle manure （CHA）, peat （PHA）, and leaf litter （LHA） as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy （XAS） was used to examine the coordination environment of the Cu（ll） adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy （NMR）. The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu（ll） on CHA, PHA, and LHA were 229.4,210.4, and 197.7 mg g-1, respectively. The adsorption of Cu（Ⅱ） on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH〉7. The adsorption of Cu（Ⅱ） was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L-1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L-1 NaNO3. The Cu（Ⅱ） adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu（Ⅱ） concentrations of 15 to 40 mg L 1. For all the Cu（Ⅱ） adsorption samples, each Cu atom was surrounded by 40/N atoms at a bond distance of 1.95 A in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu（Ⅱ） was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu（Ⅱ） was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu（Ⅱ）. These results are important to achieve better understanding of the behavior of Cu（Ⅱ） in soil and water bodies in the presence of organic materials.

Synthesis, Crystal Structure and Fluorescent Property of a New One-dimensional Cadmium(Ⅱ) Coordination Polymer Based on 3,4-Thiophenedicarboxylic Acid and 1,10-Phenanthroline

A new cadmium（Ⅱ） polymer [Cd（tdc）（Phen）]n 1 （H2tdc = thiophene-3,4-dicar-boxylic acid, Phen = 1,10-phenanthroline） was synthesized under hydrothermal conditions. The compound crystallizes in the triclinic system, space group P , with a = 7.3150（10）, b = 10.3598（14）, c = 10.8784（15） , α = 82.2740（10）, β = 72.9730（10）, γ = 80.236（2）°, V = 773.68（18） 3, Z = 2, Mr = 462.74, Dc = 1.986 Mg/m3, μ = 1.58 mm-1, F（000） = 456, the final R = 0.0218 and wR = 0.0465 for 3361 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The compound presents a one-dimensional （1-D） double-stranded structure and exhibits fluorescent emission at room temperature. Furthermore, infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of the compound are also investigated.

Synthesis,Crystal Structure and Theoretical Calculations of a Nickel(Ⅱ) Coordination Polymer Assembled by 4,4'-Oxydibenzoic Acid and 1,3-Bis(imidazol-1-ylmethyl)-benzene Ligands

A new metal-organic coordination polymer [Ni（oba）（mbix）（H2O）]n·n H2O（H2oba = 4,4‘-oxydibenzoic acid,mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Green crystals crystallize in the triclinic system,space group P1 with a = 10.1915（18）,b = 11.415（2）,c = 12.314（2）A,α = 74.263（3）,β = 84.545（2）,γ = 74.369（3）o,V = 1327.6（4） A,C28H26N4 Ni O7,Mr = 589.24,Dc = 1.474 g/cm3,F（000） = 612,Z = 2,μ（Mo Kα） = 0.786 mm-1,the final R = 0.0332 and w R = 0.0869 for 4622 observed reflections（I 〉 2σ（I））.The structure of 1 exhibits a one-dimensional chain-like structure.In addition,natural bond orbital（NBO） analysis was performed by the PBE0/LANL2 DZ method in Gaussian 03 Program.The calculation results show obvious covalent interaction between the coordinated atoms and Ni（Ⅱ） ion.

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Nickel(Ⅱ) Complex with 2-Pyridinecarboxyic Acid and 4,4′-Bipyridine Ligands

A new metal-organic coordination polymer [Ni[（2-pya）2（4,4′-bipy）]n·6nH2O （2-pya = 2-pyridinecarboxylic acid, 4,4′-bipy = 4,4′-pyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I4 1/α with a = b = 22.5642（19）, c = 10.7118（18） A, V = 5453.8（11） A^3, C22H28N4NiO10, Mr= 567.19, Dc = 1.382 g/cm^3, μ（MoKα） = 0.769 mm^-1, F（000） =2368, Z = 8, the final R = 0.0572 and wR = 0.1254 for 1401 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure by mixed ligands of 2-pyridinedicarboxylic acid and 4,4′-pyridine.

Direct Spectroscopic Determination of Europium（ Ⅱ ） Concentration During Europium（ Ⅲ ） Electro-Reduction in Hydrochloric Acid Medium

UV-Vis spectroscopy was used to directly determine the concentration of Eu（ Ⅱ） during electroreduction of Eu （ Ⅲ ） in hydrochloric acid medium. Electroreduction was carried out in a flow type electrolyzer with glassy carbon cathode at the constant potential of - 800 mV vs. Ag/AgCl. The effects of oxygen and concentration of hydrochloric acid on the system were investigated. For 0.01 mol· L^-1 hydrochloric acid, calibration curves for Eu （Ⅱ） absorption bands at 248 and 320 nm were constructed. Molar absorption coefficients were estimated to be 2016 and 648 L· mol^-1·cm^-1, respectively. The absorbance strongly decreased with decrease in pH of the solution, whereas concentration of chloride had only a negligible effect.

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.

Synthesis,Crystal Structure and Theoretical Calculations of a Zinc(Ⅱ) Coordination Polymer Assembled by Pyrazine-2,3-dicarboxylic Acid and Bis(imidazol) Ligands

A new metal-organic coordination polymer [Zn（pzdc）（mbix）]n·nH2O（H2pzdc = pyrazine-2,3- dicarboxylic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a = 8.5519（6）, b = 14.8764（10）, c = 16.4108（11） A, β = 103.4520（10）o, V = 2030.5（2）A^3, C（20）H（18）N6O5Zn, Mr = 487.77, Dc = 1.596 g/cm^3, F（000） = 1000, Z = 4, μ（MoK α） = 1.257 mm^-1, the final R = 0.0260 and w R = 0.0706 for 3445 observed reflections（I 〉 2σ（I））. The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital（NBO） analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn（Ⅱ） ion.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.