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.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Degradation of Acid Orange 7 by electrochemically generated (*)OH radicals in acidic aqueous medium using a boron-doped diamond or platinum anode: a mechanistic study

A comparative study of the degradation of Acid Orange 7 (AO 7) aqueous solutions in acidic medium of pH 3.0 by electro-Fenton process using Pt or boron-doped diamond (BDD) anode was reported. The oxidative degradation of AO 7 by electrochemically generated hydroxyl radicals follows a pseudo-first order kinetic with a similar rate constant with BDD or Pt anode. The absolute rate constant of the AO 7 hydroxylation reaction was determined as (1.10+/-0.04)x10(10)M(-1)s(-1) by using the competition kinetic method. The comparative study of TOC measurements during electro-Fenton treatment showed a higher mineralization rate with BDD than Pt anode at the first hours of electrolysis because of the higher oxidizing power of this anode. The electro-Fenton degradation of AO 7 was followed by monitoring the formation and evolution of aromatic intermediates which are oxidized to aliphatic carboxylic acids before mineralization (transformation to CO(2) and inorganic ions, i.e. sulphate, nitrate and ammonium). The follow-up of the solution toxicity evolution shows the formation of intermediates more toxic than AO 7 and the connection between toxicity and aromaticity. A mineralization reaction pathway of AO 7 by electro-Fenton degradation involving all the intermediates identified was proposed.     

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.     

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrodes

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30 000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm⁻². Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k_app close to 3.2 × 10⁻² min⁻¹. The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities ?150 mA cm⁻². The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition.     

Electrochemical treatment of domestic wastewater using boron-doped diamond and nanostructured amorphous carbon electrodes

The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H₂O₂) using amorphous carbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H₂O₂ (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphous carbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8 %, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9 %, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9?±?2 and 85.5?±?2 %, whereas 70 % of total organic carbon removal was achieved.     

Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode

Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID > QL > IQL > BT > BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results.     

Electrochemical mineralization and detoxification of naphthenic acids on boron-doped diamond anodes

Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m² and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m² of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC₅₀ towards Vibrio fischeri) after 2 h of treatment.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

掺硼金刚石三电极系统处理垃圾渗滤液实验研究

实验以掺硼金刚石电极为阳极构建三电极系统处理稳定的垃圾渗滤液.考察了稀释比、初始pH值、电流密度和极板间距4个因素对垃圾渗滤液污染物去除率的影响.实验结果表明,电流密度、稀释比是影响电化学氧化垃圾渗滤液的主要因素,极板间距、初始pH值对电化学氧化垃圾渗滤液的影响较小.在稀释比为1:2、电流密度为75 mA/cm2、pH值未调节、极板间距为10 mm最优工况时,经过5 h电化学氧化后NH4+-N、COD均能完全去除;NH4+-N、COD去除率分别满足线性方程y =21.759t、y =20.717t,对应的线性相关系数为0.9923和0.9925.最优工况条件下,BDD电极电化学氧化垃圾渗滤液的能耗为260 kWh/m3.     

Anodic oxidation of benzoquinone using diamond anode

The anodic degradation of 1,4-benzoquinone (BQ), one of the most toxic xenobiotic, was investigated by electrochemical oxidation at boron-doped diamond anode. The electrolyses have been performed in a single-compartment flow cell in galvanostatic conditions. The influence of applied current (0.5–2 A), BQ concentration (1–2 g dm^?3), temperature (20–45 °C) and flow rate (100–300 dm³ h^?1) has been studied. BQ decay kinetic, the evolution of its oxidation intermediates and the mineralization of the aqueous solutions were monitored during the electrolysis by high-performance liquid chromatograph (HPLC) and chemical oxygen demand (COD) measurements. The results obtained show that the use of diamond anode leads to total mineralization of BQ in any experimental conditions due to the production of oxidant hydroxyl radicals electrogenerated from water discharge. The decay kinetics of BQ removal follows a pseudo-first-order reaction, and the rate constant increases with rising current density. The COD removal rate was favoured by increasing of applied current, recirculating flow rate and it is almost unaffected by solution temperature.     

Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH,applied current intensity and electrolyte

The anodic oxidation of tetracycline was performed in an up-flow reactor, operating in batch mode with recirculation, using as anode a boron-doped diamond electrode. The influence on the degradation rate of solution initial pH (2 to 12), applied current intensity (25 to 300 A m^?2) and type of electrolyte (sodium sulphate or sodium chloride) were investigated. For the assays run at equal current density, with sodium sulphate as electrolyte, the solution’s initial pH of 2 presented the highest absorbance and chemical oxygen demand removals. Regarding the influence of current density, for equal charge passed, the organic load removal rate decreased with the increase in applied current. When sodium sulphate was used as an electrolyte, high-performance liquid chromatography (HPLC) results have shown an almost complete removal of tetracycline after a 2-h assay. HPLC results have also shown the presence of oxamic acid as one of the intermediates of tetracycline anodic oxidation. The complete removal of tetracycline was much faster in the presence of chloride ions that promoted the complete degradation of this antibiotic in 30 min. However, in the presence of chloride ions, the tetracycline mineralization is slower, as observed by the lower organic carbon removal rate when compared to that of the tetracycline degradation in the presence of sulphate.     

因子设计法优化掺硼金刚石电催化降解染料废水

掺硼金刚石电催化工艺(BDD工艺)作为当前热门的水处理技术,已被成功用于降解多种有机污染物。采用因子设计方法,考查了BDD工艺对偶氮染料金橙-Ⅱ的降解效能。实验选用染料初始浓度、反应时间、电解质浓度、施加电流和流速作为操作参数,并以脱色率作为响应指标来评估各参数的统计学显著性。在考察的5个因素中,前两者对于处理效果具有最为显著的影响。为此,在高因子水平情况下又进一步分析了它们的主效应和相互效应,同时构造了回归模型。实验结果表明,因子设计法对于优化BDD工艺是非常适用的,并显示了其实际应用的前景。     

掺硼金刚石薄膜电极在水处理中应用的研究进展

掺硼金刚石(BDD)薄膜电极作为一种新型的电极材料,在水溶液中电解时具有较宽的电位窗口,在浓酸浓碱中具有很好的耐腐蚀性,其表面不易吸附污染物,与它的同素异构体电极及其他普通电极相比,具有更好的化学、物理性能,从而表现出潜在的功能,近年来被科研人员用于废水处理,并取得了很好的处理效果,对近期BDD薄膜电极的制备、在污水处理中的应用及其进展进行了总结与讨论.     

运用BDD电极优化废水中氨氮的直接电化学检测方法

针对高氨氮条件下离子选择电极稳定性差的问题,筛选了3种市售硼掺杂金刚石(BDD)电极,以探究直接电化学检测氨氮的可行性.采用极化曲线法测试了3种BDD电极的析氧、析氢和析氯电位,以获得最佳电势窗口.采用循环伏安法研究了氨氮在3种BDD电极上的氧化还原行为,在1.6 V处发现了明显的氨氮氧化峰,可为氨氮直接检测提供定性依...     

Ozonation of o-cresol in aqueous solutions using a rotating packed-bed reactor.

Experimental results indicated that ozone transfer in the rotating packed contactor was noticeably greater than in a traditional packed-bed contactor under similar operational conditions. Ozonation in the rotating packed contactor has been shown to be feasible for achieving nearly complete decomposition of o-cresol within 1 hour. The decomposition of o-cresol by ozonation in the rotating packed contactor increased with increasing rotor speed and decreasing the gas-liquid flowrate ratio. However, the reduction of total organic carbon during the ozonation of o-cresol was not influenced by variation of rotor speed and gas-liquid flowrate ratio. The species distribution of o-cresol under various solution conditions plays a significant role in determining the decomposition behavior. In most experiments conducted in this study, the decomposition of o-cresol by ozonation was more favorable under alkaline conditions.     

Electrochemical removal of synthetic textile dyes from aqueous solutions using Ti/Pt anode: role of dye structure

In this work, the efficiency of electrochemical oxidation (EO) was investigated for removing a dye mixture containing Novacron Yellow (NY) and Remazol Red (RR) in aqueous solutions using platinum supported on titanium (Ti/Pt) as anode. Different current densities (20, 40 and 60 mA cm^?2) and temperatures (25, 40 and 60 °C) were studied during electrochemical treatment. After that, the EO of each of these dyes was separately investigated. The EO of each of these dyes was performed, varying only the current density and keeping the same temperature (25 °C). The elimination of colour was monitored by UV-visible spectroscopy, and the degradation of organic compounds was analysed by means of chemical oxygen demand (COD). Data obtained from the analysis of the dye mixture showed that the EO process was effective in colour removal, in which more than 90 % was removed. In the case of COD removal, the application of a current density greater than 40 mA cm^?2 favoured the oxygen evolution reaction, and no complete oxidation was achieved. Regarding the analysis of individual anodic oxidation dyes, it was appreciated that the data for the NY were very close to the results obtained for the oxidation of the dye mixture while the RR dye achieved higher colour removal but lower COD elimination. These results suggest that the oxidation efficiency is dependent on the nature of the organic molecule, and it was confirmed by the intermediates identified. Figure

Chemical structures of a NY and b RR