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 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.     

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.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

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.     

电絮凝处理腐殖酸过程中阳极钝化影响因素分析

针对电絮凝(electrocoagulation,EC)处理腐殖酸(humic acid,HA)过程中电极易发生钝化,造成处理效能下降的问题,主要探究了阳极表面粗糙度、初始pH、初始HA浓度对于铝阳极钝化的影响,随后通过检测溶液中残留Al³⁺浓度和阳极板表面形貌,进一步分析了HA浓度对于铝阳极钝化发展的影响机制。结果表明：铝阳极钝化程度与阳极板表面算数平均粗糙度(arithmetic mean roughness,Ra)呈负相关,随着Ra从2 055 nm下降到270 nm,阳极板的电荷转移电阻(charge transfer resistor,Rct)从1 174.0 Ω·cm²增大到1 481.2 Ω·cm²;当溶液初始pH从3 提高到 7 时,极板的Rct从461.0 Ω·cm²增大到1 120.2 Ω·cm²,而当pH继续升高到 9 时,极板的Rct下降到169.5 Ω·cm²;铝阳极钝化程度随溶液初始HA浓度呈现先减小后增大的规律。HA的质量浓度从0 mg·L⁻¹ 提高到20 mg·L⁻¹ 时,对应极板的Rct从1 536.4 Ω·cm²减小到932.9 Ω·cm²,HA的质量浓度进一步上升至200 mg·L⁻¹时,对应极板的Rct又从932.9 Ω·cm²增大到1 403.2 Ω·cm²。本研究结果可为EC在实际应用中抑制阳极钝化提供参考。     

电催化氧化处理三唑类杀菌剂模拟废水

以三环唑和丙环唑为特征污染物,研究了TiO2-NTs/SnO2-Sb/PbO2电极电催化氧化处理模拟废水中三唑类杀菌剂的机理。实验结果表明,电催化氧化对废水中三唑类杀菌剂的降解符合一级动力学关系,且降解速率为:丙环唑>三环唑。利用气相色谱-质谱联用仪(GC-MS)和离子色谱仪(IC)对电催化氧化降解三环唑和丙环唑溶液产生的中间产物和最终产生的有机酸和无机离子进行检测分析,推断出废水中三唑类杀菌剂电催化氧化的降解路径。通过斑马鱼实验得出电催化氧化对废水中三环唑急性毒性的削减幅度较大,对丙环唑的削减幅度较小。     

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.     

阳极石墨毡酸处理对微生物燃料电池型BOD传感器性能的影响

通过石墨毡表面润湿性的变化,确定了硝酸酸化处理石墨毡的操作条件。采用硝酸处理后的石墨毡作为电极材料,构建双室无介体微生物燃料电池(microbial fuel cell,MFC)型BOD传感器,并对BOD传感器的性能进行评价。结果表明,硝酸酸化处理明显提高石墨毡表面的润湿性,经过4 h酸化处理,石墨毡的表面接触角由142.5°下降到86.5°。采用硝酸处理的石墨毡作为电极材料,MFC的电流输出明显提高且稳定,在响应时间小于10 h条件下,废水BOD检测上限为100 mg/L。废水BOD浓度在2~50 mg/L范围内,可以利用BOD浓度与电流最大值之间的线性关系进行废水BOD浓度检测,废水BOD浓度在2~100 mg/L范围内,可以利用BOD浓度与电荷量之间的线性关系对废水BOD浓度进行检测,检测相对误差均在12%以下。MFC型BOD传感器运行稳定,相对标准偏差均在10%以下。