Electrocatalytic reduction of nitrate ions from water using polyaniline nanofibers modified gold electrode

Polyaniline (PANI) nanofibers were electrochemically synthesized on gold electrode using ethanol as soft template by the cyclic voltammetry technique. The PANI nanofibers were characterized by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and scanning electron microscopy. Linear sweep voltammetry was used to investigate electrocatalytic activity of the PANI nanofibers modified electrode toward the reduction of nitrate ions. Results showed that the electroreduction process strongly depends on the applied potential. At the potential value of about -0.8 V vs Ag/AgCl, the electroreduction of nitrate anions to nitrite anions was identified as the rate-determining step of the electroreduction process. In the potential range of -0.8 to -1.0 V, reduction of nitrite to hydroxylamine occurs, followed by the reduction to ammonia. At potentials more negative than -1.0 V, nitrite is directly reduced to ammonia. This study demonstrates the effectiveness of PANI nanofibers modified electrode in the electroreduction of nitrate ions compared to traditional reduction methods.     

Electrochemical dechlorination of chloroacetic acids (CAAs) using hemoglobin-loaded carbon nanotube electrode

Hemoglobin (Hb) was immobilized on carbon nanotube (CNT) electrode to catalyze the dechlorination of chloroacetic acids (CAAs), and the electrocatalytic behaviors of the Hb-loaded electrode for the dechlorination of trichloroacetic acid (TCAA) were studied by cyclic voltammetry and constant-potential electrolysis technique. An Hb-loaded packed-bed flow reactor was also constructed for bioelectrocatalytic dechloriantion of CAAs from drinking water. The results showed that the reduced heme of Hb immobilized on CNT electrode was easily regenerated, and Hb exhibited a stable and high activity for reductive dechlorination of CAAs with significant lowering of overpotential. TCAA could be reduced at -0.450 V (vs. saturated calomel electrode (SCE)) with catalysis of Hb-loaded electrode and its dechlorination was stepwise, following the pathway of TCAA-->dichloroacetic acid (DCAA)-->monochloroacetic acid (MCAA)-->acetic acid. It was also found that all CAAs, e.g., TCAA, DCAA and MCAA, could be dechlorinated completely at -0.450 V. The removal of 30.0 mM TCAA and DCAA is ca. 40% and 31%, respectively, with electrolysis for 100 min at -0.600 V (vs. SCE) using the Hb-loaded packed-bed flow reactor. The dechlorination activities of CAAs follow the decreasing order: TCAA>DCAA>MCAA, and the average current efficiency is over 90%.     

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

Voltammetric detection of trifluralin in tap water,fruit juice,and vegetable extracts in the presence of surfactants

This study describes a novel electrochemical method to determine the herbicide trifluralin in samples of water, fruit juice, and vegetable extracts in the presence of surfactants, using a glassy carbon electrode (GCE). In acidic media, trifluralin was irreversible on the glassy carbon electrode surface at ?0.5 V vs. Ag/AgCl. Surfactant presence on the electrode–solution interface modified current intensities and shifted the reduction peak potential of trifluralin. Different types of surfactant and their concentrations were investigated. The anionic surfactant significantly enhanced the peak current intensity of trifluralin. Under optimal analytical conditions, an analytical curve was obtained in the concentration range of 0.48–32.20 µM. The limits of detection and quantification were estimated at 0.031 and 0.104 µM, respectively. The method was successfully applied to quantify trifluralin in samples of water, orange and tomato juice, and green pepper, carrot, and onion extracts, with recovery rates of 97.9–102.1%. The results were in good agreement with those obtained using high-performance liquid chromatography, indicating that the proposed electrochemical method can be employed to quantify trifluralin in various types foods, with sensitivity, specificity, selectivity and reproducibility.     

Removal of methyl parathion from water by electrochemically generated Fenton's reagent

The electro-Fenton process was used to assess the degradation of methyl parathion (MP) in aqueous solutions. This oxidation process allows the production of hydroxyls radicals which react on the organic compounds, leading to their mineralization. Degradation experiments were performed either in perchloric, sulphuric, hydrochloric and nitric acid media under current controlled electrolysis conditions at different pH. The pH effect as well as the nature of the medium (i.e., the nature of the ions present in medium) on the degradation and mineralization efficiency were studied. The mineralization of the initial pollutant was investigated by total organic carbon measurements which show a complete mineralization at pH 3 in perchloric medium. The absolute rate constant of MP hydroxylation reaction was determined as (4.20+/-0.11)x10(9)M(-1)s(-1). Complete degradation of MP and its metabolites occur in less than 45min. Degradation reaction intermediates such as aromatic compounds, carboxylic acids and inorganic ions were identified and a mineralization pathway is proposed.     

Electrocatalytic oxidation of methyl tert-butyl ether (MTBE) in aqueous solution at a nickel electrode

This study utilized the electrocatalytic characteristics of nickel electrode to perform degradation of methyl tert-butyl ether (MTBE) in aqueous solution. Lab experiments were conducted in a spiltless bath type cell equipped with a nickel electrode as working electrode, a platinum wire as counter electrode, and an Ag/AgCl electrode as reference electrode. Effects of controlled potential, supporting electrolyte, and solution pH on the efficiency of MTBE removal were examined under the control of the constant-potential conditions. Experiment results showed that the optimum electrolytic condition was operated at 0.35 V in a 1M KOH electrolyte solution, and the initial 20 mgl(-1) MTBE was reduced by 73% within 180 min under the optimum control. As using 1M Na2SO4 and 1M KCl as electrolyte, the efficiency of MTBE removal dropped to 60% and 50% under the similar controls. Comparing with various pH controls, the strong basic condition is favorable for electrocatalytic oxidation of MTBE in the Ni-electrolytic system. The efficiency of MTBE removal showed a rising trend with increasing initial pH of the solution. The formation of a redox NiOOH/Ni(OH)2 layer on the anode surface, which was observed on the SEM image, can explain that nickel plays a mediator role on improving electrocatalytic oxidation of MTBE at 0.35 V in a strong basic condition. The by-products of MTBE degradation were identified as acetone and CO(2) by GC/MS, and the distributions of carbon atoms in acetone, CO2, and MTBE were found 22%, 51%, and 27% through the optimum control of electrochemical oxidation.     

三维过电位电解处理罗丹明B废水

选用钛基RuO2-TiO2涂层电极作为三维过电位电解装置的阳极,紫铜作为阴极,活性炭作为第三极,研究了三维过电位电解处理罗丹明B废水的效果,并考察了外加电压、电解时间、初始浓度、pH值和搅拌方式等因素对其处理效果的影响。实验结果表明,外加电压、电解时间和初始浓度等因素均对罗丹明B的降解效果有影响,而pH值、搅拌方式等对罗丹明B的降解效果基本没有影响。与二维电解的对比研究表明,在罗丹明B溶液初始浓度为20mg／L,电解时间为1h,电解电压为20V时,采用二维电解的降解率为20％左右,而三维过电位电解的降解率接近80％。最终产物分析结果显示,经过处理的罗丹明B苯环开环变成直链烃类物质,或者饱和环状有机物,不再具有生物毒性,适合后续的生化处理。     

A voltammetric screening method to determine ronidazole in bovine meat

Abstract

An original voltammetric screening method, employing glassy carbon electrode (GCE) with the differential-pulse voltammetry technique (DPV), has been developed to determine residues of the anti-parasitic agent Ronidazole (RNZ) in bovine meat. By using cyclic voltammetry (CV), it has been demonstrated that an irreversible cathodic process occurs at approximately ?0.740?V (vs. Ag|AgCl, KCl 3?mol L^?1) in a 0.100?mol L^?1 phosphate buffer at pH 6.5 as supporting electrolyte. Furthermore, the behavior of RNZ in CV indicates the occurrence of a diffusion mass transfer process to the working electrode surface. The RNZ reduction mechanism was proposed as a 6-electron transfer, similar to Metronidazole under the same pH range. Quantification of RNZ and method validation were then carried out by DPV. The relative standard deviation (RSD) were 3.21% for intraday precision of 10 consecutive repetitions and 6.78% for interday precision after five analysis. Limits of detection and quantification were also obtained, and the values were 0.107 and 0.358?mg kg^?1, respectively. The recovery percentage for three different concentrations of RNZ in the bovine meat matrix ranged between 98.1% and 100.3%. The method proved to be efficient for screening RNZ in bovine meat.     

三维电极法深度处理维生素生产废水

采用三维电极法对维生素废水进行深度处理,分别以钛涂钌铱板、铁板和不锈钢板作为电极阳极,石墨板作为电极阴极,柱状活性炭作为粒子电极,结果表明,当以钛涂钌铱板作为阳极,以粒径为1 mm的柱状活性炭作为粒子电极时电解效果最好,COD和色度去除率最高。实验选择电解电压、电极板间距、电解时间和初始pH值作为主要影响因素进行正交实验,实验研究证明,各因素的影响大小为电解电压>电极板间距>电解时间>初始pH值,得到的最佳参数组合分别为:电解电压为10 V,电极板间距为8 cm,电解时间为20 min,初始pH值为4,得到COD和色度最大去除率分别为59.5%和93.57%。     

Nylon 6,6 modified screen printed carbon electrodes as electrochemical sensors for rapid chlorothalonil determination in water samples using differential pulse cathodic stripping voltammetry

A newly developed electrochemical sensor for chlorothalonil based on nylon 6,6 film deposited onto screen printed electrode (SPE) with electrochemical modulation of pH at the electrode/solution interface was studied for the first time. Differential pulse cathodic stripping voltammetry (DPCSV) was used to carry out the electrochemical and analytical studies. Experimental parameters such as accumulation potential, initial potential, accumulation time and pH of Britton-Robinson buffer have been optimized. Chlorothalonil gave optimum analytical signal in a medium of 0.04?M Britton-Robinson buffer at pH 6.0. A well-defined reduction peak was observed, at E_p= ?0.851 and ?0.938?V vs. Ag/AgCl (3.0?M KCl) for both bare SPE and modified SPE, respectively. The peak currents of modified SPE were significantly increased as compared to bare SPE. At the modified SPE, a linear relationship between the peak current and chlorothalonil concentration was obtained in the range from 0.1 to 2.8?×?10^?6?M with a detection limit of 1.53?×?10^?8?M (S/N=?3). The practical applicability of the newly developed method has been demonstrated on analyses of real water samples. The newly developed sensor shows good reproducibility with RSD of 3.92%. The nylon 6,6 modified SPE showed itself as promising sensor with good selectivity for chlorothalonil determination.     

Performance of three-phase three-dimensional electrode reactor for the reduction of COD in simulated wastewater-containing phenol

The removal of chemical oxygen demand (COD) from wastewater-containing phenol was investigated using three-phase three-dimensional electrode reactor. Special attention was paid to experimentally probe the performance of the reactor in COD removal in the process of repeated batch runs. The experimental results showed that the reactor could remove COD from phenol-containing wastewater much more efficiently than both granulated activated carbon (GAC) adsorption bed and conventional three-dimensional electrode. For 200th batch run, the three-phase three-dimensional electrode reactor with an airflow of 5 l min(-1) and a cell voltage of 30 V could remove 1350 ppm COD from the wastewater in 30 min while conventional three-dimensional electrode reactor with a same cell voltage and GAC adsorption bed with a same airflow only could remove 610 and 1000 ppm, respectively, at the same reaction duration. Although it was found that COD removal decreased with increasing repeated batch runs in our experimental range, due to adsorption saturation of GAC and electrode passivation, the extent of decrease for the three-phase three-dimensional electrode is much less than those for conventional three-dimensional electrodes and GAC adsorption beds. The passivated reactor could be partly re-activated by electrolysis in the presence of MnO2.     

活性炭三维电极法处理超高盐榨菜腌制废水

将粒状活性炭作为三维电极的粒子电极处理超高盐榨菜腌制废水。采用静态实验,对比了二维电极与三维电极对该废水COD和磷酸盐的去除效果,考察了三维电极条件下极板间距、活性炭填充量、电解时间、电解电流及初始pH等对该废水COD和磷酸盐去除率的影响。结果表明：三维电极对超高盐榨菜腌制废水COD和磷酸盐的去除率明显高于二维电极;在原水pH（4．3—5．0）,废水体积600mL,电流8A,活性炭填充量250g,极板间距6．5cm,电解时间150min时,处理效果良好,COD和磷酸盐去除率分别为76．47％和97．81％。由波长扫描图可初步认为部分有机物直接被氧化为二氧化碳。     

Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

Behavior of bromide in the photoelectrocatalytic process and bromine generation using nanoporous titanium dioxide thin-film electrodes

In this study, the photoelectrocatalytic behavior of bromide and generation of bromine using TiO2 was investigated in the separate anode and cathode reaction chambers. Our results show that the generation of bromine begins around a flatband potential of -0.34 V vs. standard calomel electrode (SCE) at pH 3.0 under UV illumination and increases with an increase in positive potential, finally reaching a steady-state concentration at 1.0 V vs. SCE. Maximum bromine formation occurs over the range of pH 4-6, decreasing sharply at conditions where the pH>7.     

Evaluation of the efficiency of monopolar and bipolar BDD electrodes for electrochemical oxidation of anthraquinone textile synthetic effluent for reuse

The efficiency of the electrochemical degradation of synthetic wastewater containing an anthraquinone dye has been comparatively studied in two electrolytic cells with a synthetic boron-doped diamond (Si/BDD) as an anode. The first is an individual cell (Cell 1) with monopolar electrode BDD and the second (Cell 2) has two bipolar electrodes BDD self-polarized. The bulk electrolysis was performed at the same initial operating conditions in order to quantify the influence of the initial pH and current density on dye discoloration and global mineralization removal. The current efficiency and the consumption energy were also evaluated. When the same solutions have been comparatively treated with the two cells, a quite good mineralization is found in Cell 2. This result supposed more fraction of the applied current is used for the electrocombustion reaction on Cell 2 if compared to Cell 1 and small amount rest for the side reaction of oxygen evolution. The HPLC analyses confirmed this hypothesis and showed that the concentration trend of intermediates (sulfanilic acid, phthalate acid and salicylic acid) with electrolysis time was different on two cells. Phototoxicity tests show that the electrochemical oxidation with BDD electrodes could be useful as a pretreatment technique for reducing hazardous wastewater toxicity.     

垃圾渗滤液生化出水的脱色研究

分别采用脉冲电解法、混凝沉淀法、芬顿氧化法、高铁酸钾氧化法对垃圾渗滤液生化出水进行处理,考察了处理效果。结果表明：铁电极电解法和芬顿试剂氧化法均能脱除垃圾渗滤液的色度,去除有机物质。铁电极电解对色度的去除率可达98．4％,COD去除率可达84．4％;芬顿试剂氧化对色度的去除率可达99％,COD去除率可达85．8％。两种方法均能使出水达到排放标准。同时比较了各种处理方法的运行成本,在达到同样出水标准的前提下,铁电极电解运行成本远低于芬顿试剂氧化,为3．67元／t水,而芬顿试剂药剂成本为8．67元／t水。     

Improved vacuum-UV (VUV)-initiated photomineralization of organic compounds in water with a xenon excimer flow-through photoreactor (Xe2* lamp, 172 nm) containing an axially centered ceramic oxygenator

Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.     

Degradation of the textile dyes Basic yellow 28 and Reactive black 5 using diamond and metal alloys electrodes

Basic yellow 28 (SLY) and Reactive black 5 (CBWB), which are respectively methine and sulfoazo textile dyes were individually exposed to electrochemical treatment using diamond-, aluminium-, copper- and iron-zinc alloy electrodes. The generated current was registered with time during electrolysis of the dye solutions and the color variation and the formation of degradation products were followed using HPLC with diode array detection. Four different electrodic materials were tested by applying different potentials in the range -1.0 to -2.5 V and presented 95% color removal and COD removal of up to 65-67% in the case of CBWB dye solution treated with the copper and iron electrodes. Efficiency was enhanced with stirring and flow in relation to the stationary regime. The kinetic parameter reaction rate was used to establish the effect of flow, potential, electrode nature and pH. The formation and characterization of the precipitate formed under certain conditions is reported and discussed.