硼掺杂金刚石膜电极电催化降解环己酮废水

采用循环伏安法、稳态极化法等对硼掺杂金刚石薄膜电极的电化学性能及电氧化降解含环己酮模拟废水的电极过程进行了研究,考察了电流密度、支持电解质浓度、起始环己酮浓度和pH值等因素对硼掺杂金刚石薄膜电极电氧化降解含环己酮模拟废水效果的影响。实验结果表明,硼掺杂金刚石薄膜电极能够对环己酮进行有效且稳定的降解,通过正交优化实验,得到较优工艺条件为阳极电流密度为5 mA·cm^-2,pH值为7,Na₂SO₄浓度为10 g·L^-1,起始环己酮浓度为20 mmol·L^-1,在该条件下COD去除率达92.95%,电流效率达80.81%,降解效果显著。     

硼掺杂金刚石膜电极电氧化降解对氯苯酚废水

采用循环伏安法研究了中性介质中对氯苯酚在硼掺杂金刚石(BDD)膜电极上的电氧化行为。提出了一种以BDD膜电极为阳极的电化学氧化降解对氯苯酚废水的新工艺,考察了阳极电流密度、对氯苯酚初始浓度、电解液初始pH、支持电解质浓度等工艺因素对电氧化降解效果的影响。结果表明:在阳极极化电位为1.4～1.6V(vs.SCE)时,对氯苯酚在BDD膜电极表面发生直接电氧化反应,生成易吸附的中间产物,导致电极活性降低;在阳极极化电位高于2.0V(vs.SCE)时,BDD膜电极能够良好地电氧化降解对氯苯酚溶液,该过程是通过直接电氧化过程与间接电氧化过程联合作用实现的。通过考察若干工艺因素对对氯苯酚电氧化降解效果的影响发现,较为理想的工艺参数组合为,阳极电流密度60mA·cm-2、支持电解质浓度10g·L-1、对氯苯酚初始浓度10mmol·L-1、电解液初始pH7。在该工艺条件下,COD去除率达到96.1%,平均电流效率为50.2%。高效液相色谱证实了BDD膜电极能有效地电氧化降解对氯苯酚。     

掺硼金刚石电极处理双酚A模拟废水的研究

以双酚A(BPA)为代表的环境内分泌干扰物的广泛使用带来了环境污染和生态健康风险。本实验以BPA为研究对象,对比了BDD电极、Ru O2电极与自制的Ti/Sn O2-Sb和Ti/Sn O2-Sb/Pb O2电极在硫酸钠电解质中电催化降解BPA的效果,研究了电流密度、电解质浓度等因素对BPA降解的影响。结果表明,BDD电极相比于Sn O2、Pb O2和Ru O2电极,对内分泌干扰物BPA电化学处理效果更好;以BDD电极为阳极,Ti板为阴极,电流密度为5m A/cm2,电解质浓度为0.05M Na2SO4时,20mg/L的BPA溶液在两小时内的去除率达到90%以上,TOC的去除率达到56%左右;电流密度增大,去除效果提高,但是电流效率下降;增加Na2SO4的浓度有助于BPA的降解过程。     

BDD电极降解酸性橙Ⅱ染料废水研究

选用掺硼金刚石(BDD)电极作为阳极、不锈钢电极阴极,对酸性橙II染料废水进行电化学降解研究。讨论了电解质、电流密度、溶液pH、初始浓度等工艺参数对酸性橙II降解速率的影响,对降解过程中染料分子的矿化进行了监测分析,并且考察了不同初始浓度下电解过程中的表观电流效率。结果表明,溶液中存在氯离子有助于酸性橙II的快速降解;以硫酸钠为电解质时,高电流密度和碱性pH环境有助于提高酸性橙II降解速率。电化学降解过程中,BDD电极可以迅速的破坏染料分子显色基团使其褪色,并无选择性的矿化各种中间产物。随着电解反应的持续进行,表观电流效率逐渐降低;污染物浓度越高,电解过程中电流效率越高。在初始浓度50 mg/L、氯化钠添加量0.01 mol/L、电流密度10 mA/cm2、初始pH 6.5左右的条件下,酸性橙II在30 min内被完全降解,120 min后TOC去除率达到96%。     

BDD阳极去除水中阿特拉津的特性及机理研究

阳极氧化技术作为最简单的高级氧化技术,可有效去除水中残留的除草剂等持久性有机污染物。利用硼掺杂金刚石（BDD）电极作为阳极构建了阳极氧化体系,研究了电解质种类、浓度和电流密度等参数对BDD阳极降解三嗪类除草剂阿特拉津效能的影响规律,并利用UPLC-MS/MS对阿特拉津的降解产物进行了定性分析。结果表明,在NaCl投加量...     

不同基底BDD电极对模拟染料废水的降解脱色试验

在Si、Ta、SiC、Ti四种不同的基底上通过热丝化学气相沉积法分别生长了掺硼金刚石（BDD）薄膜。试验对BDD膜层的微观形貌、电极的电化学性能进行了研究。四种基底的BDD电极均具有较宽的电位窗口;Ta—BDD和SiC—BDD晶体形貌完整;Ta—BDD和Ti—BDD具有较好的膜基附着力,具有较长的寿命。试验表明,使用12h后,Ta—BDD与Ti—BDD仍具有良好的电解性能,微观形貌完整,而Si—BDD和SiC—BDD分别使用4h和6h后,膜层便开始脱落。试验测定了Ta—BDD电极对活性艳红X-3B模拟染料废水的降解脱色效果,考察了不同条件（槽电压、电解质浓度、电解质种类及pH）对脱色效果的影响。结果表明：在酸性介质中,当硫酸钠浓度为2．5s／L时,经过120min电解,模拟废水中的染料可脱除至1％以下。NaCl作为支持电解质时,相比于Na2SO4对废水色度的脱除具有更强的作用。     

低电流密度下不同材质阳极电解生成过硫酸盐研究

以Si/BDD(Boron-doped diamond)、Ti/Sn O₂、Ti/Pb O₂、Ti/Pt 4种常见电极为阳极,考察其在电解Na₂SO₄生成过硫酸盐(PDS)过程中的电化学行为,以及低电流密度条件下电解质浓度,电流密度和PDS、H₂SO₄、NH₄SCN的投加对电解法制备PDS的影响。结果表明：在低电流密度条件下,生成PDS的主要途径是通过阳极电解水产生·OH来介导SO₄^2-的氧化;相同反应条件下,4种阳极中Si/BDD阳极电解体系对PDS的生成效果最佳,以Si/BDD电极为阳极,在Na₂SO₄浓度0.9 mol/L、电流密度60 m A/cm²条件下,电解60 min时生成的PDS浓度为24.12 mmol/L;提高电解质浓度和电流密度可以提高电流效率和PDS产量,向电解质中添加Na₂S     

掺硼金刚石薄膜电极电催化降解染料废水的研究

通过测试新型掺硼金刚石薄膜电极的电化学性质,发现掺硼金刚石薄膜电极具有较高的析氢析氧过电位,有效地抑制了析氧副反应,具有较高的催化氧化效率。在研究活性艳红模拟染料废水在该电极上的催化降解过程中,考察了不同工艺条件:活性炭投加、电解质、电流密度、pH值和染料废水的初始浓度对染料降解脱除的影响。实验结果表明:在酸性介质中,投加一定量的活性炭和2gL-1硫酸钠电解质,选用电流密度为0.08Acm-2,来处理高浓度染料废水色度去除率可达到99%。由染料废水处理前后的紫外可见光谱表明电解不仅破坏了染料分子中的偶氮共轭发色基团,达到去色的目的,还可以断裂其他难降解小分子基团。     

BDD阳极电活化硫酸盐降解除草剂阿特拉津的研究

用掺硼金刚石(BDD)电极对硫酸盐进行阳极活化,结果发现,在循环阳极电极模式下,BDD阳极电活化硫酸盐去除阿特拉津(ATZ)的速率较直接电解去除ATZ的速率高出约14倍。当电流密度为30 mA/cm2、Na_2SO_4电解质浓度为0.1 mol/L时,电活化硫酸盐产生的SO_4~(·-)对ATZ降解的相对贡献率可达90%以上。     

BDD电极电催化降解苯酚废水的研究

采用直流等离子体化学气相沉积方法制备了硼掺杂金刚石(BDD)薄膜电极。以苯酚为目标污染物,研究了苯酚废水在电极上的电化学降解规律及降解历程。结果表明,不同浓度的苯酚在电极上均能够完全矿化成CO2。高浓度条件下,苯酚先转化成中间产物,然后中间产物再氧化成CO2;低浓度条件下,苯酚氧化反应迅速,直接矿化成CO2。提高电流密度能够加速苯酚的降解,但会导致电流效率下降。苯酚的降解历程为对位首先受到·OH自由基的攻击,生成对苯二酚,再开环形成顺、反丁烯二酸与乙酸,然后顺、反丁烯二酸在阴极还原为丁二酸,丁二酸氧化脱羧形成丙二酸、乙酸、草酸或甲酸,最终氧化成CO2。     

准毛细间隙反应器中直接电氧化合成茴香醛二甲基缩醛

以准毛细间隙反应器为电化学合成装置,采用恒电流电解技术考察了阳极材料、支持电解质、电流密度等工艺参数对茴香醚直接电氧化合成茴香醛二甲基缩醛的影响。结果表明,收率从高到低采用的阳极材料依次为：石墨>钛基铱钽>钛基钌铱>钛基铂;支持电解质依次为：对甲基苯磺酸钠>苯磺酸钠>氟化钾>甲醇钠>高氯酸钠>间硝基苯磺酸钠;在电流密度1～9 A·dm^-2范围内,反应选择性随着电流密度的增大而减小;添加适量的2,6-二甲基吡啶能抑制茴香醛二甲基缩醛的氧化从而提高反应选择性。在优化条件下,茴香醛二甲基缩醛的收率和电流效率分别达到75%和47%。     

Influence of anode material on the electrochemical oxidation of 2-naphthol: Part 1. Cyclic voltammetry and potential step experiments

The anodic oxidation of 2-naphthol has been studied by cyclic voltammetry and chronoamperometry, using a range of electrode materials such as Ti-Ru-Sn ternary oxide, lead dioxide and boron-doped diamond (BDD) anodes. The results show that polymeric films, which cause electrode fouling, are formed during oxidation in the potential region of supporting electrolyte stability. IR spectroscopy verified the formation of this organic film. While the Ti-Ru-Sn ternary oxide surface cannot be reactivated, PbO₂ and BDD can be restored to their initial activity by simple anodic treatment in the potential region of electrolyte decomposition. In fact, during the polarization in this region, complex oxidation reactions leading to the complete incineration of polymeric materials can take place on these electrodes due to electrogenerated hydroxyl radicals. Moreover, it was found that BDD deactivation was less pronounced and its reactivation was faster than that of the other electrodes.     

Voltammetric and electrochemical impedance spectroscopy characterization of a cathodic and anodic pre-treated boron doped diamond electrode

The effect of boron doped diamond (BDD) surface termination, immediately after cathodic and anodic electrochemical pre-treatments, on the electrochemical response of a BDD electrode in aqueous media and the influence of the different supporting electrolytes utilized in these pre-treatments on the final surface termination was investigated with [Fe(CN)₆]^4−/3−, as redox probe, by cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry results indicate that the electrochemical behavior for the redox couple [Fe(CN)₆]^4−/3− is very dependent on the state of the BDD surface, and a reversible response was observed after the cathodic electrochemical pre-treatment, whereas a quasi-reversible response occurred after anodic electrochemical pre-treatment. Differential pulse voltammetry in acetate buffer also showed that the potential window is very much influenced by the electrochemical pre-treatment of the BDD surface. Electroactivity of non-diamond carbon surface species (sp² inclusions) incorporated into the diamond structure was observed after cathodic and anodic pre-treatments. Electrochemical impedance spectroscopy confirmed the cyclic voltammetry results and indicates that the BDD surface resistance and capacitance vary significantly with the electrolyte and with the electrochemical pre-treatment, caused by different surface terminations of the BDD electrode surface.     

Electrochemical oxidation of 1,4‐dioxane at boron‐doped diamond electrode

BACKGROUND: The electrochemical oxidation of 1,4‐dioxane at a boron doped diamond (BDD) surface on a niobium substrate anode was studied because (i) 1,4 dioxane is a resistant contaminant in waste‐waters and ground‐waters which needs to be removed/oxidized and (ii) most of the currently applied techniques for removal/oxidation require chemicals. RESULTS: Results show that in the potential region supporting electrolyte stability 1,4‐dioxane can be oxidized directly. Adhesive products, which cause electrode fouling, are also formed during oxidation in this potential region. The BDD anode can be restored to its initial activity by simple anodic treatment in the potential region of electrolyte decomposition. In this region, oxidation reactions leading to complete oxidation of 1,4‐dioxane, can take place due to electro‐generated hydroxyl radicals. Therefore, dioxane can only be effectively oxidized at these potentials. The effect of current density on the oxidation of 1,4‐dioxane has been investigated. The experimental results have also been compared with a theoretical chemical oxygen demand (COD)–instantaneous current efficiency (ICE) model. At a current density above 32 mA cm^?2, the oxidation process is completely controlled by mass transfer and no intermediates are formed. 92% of the COD can be removed with a total consumption of 7 Ah L^?1. CONCLUSIONS: Results show that dioxane can be effectively and completely oxidized at a BDD anode. Copyright © 2010 Society of Chemical Industry     

Electrochemical incineration of chloranilic acid using Ti/IrO2, Pb/PbO2 and Si/BDD electrodes

The electrochemical oxidation of chloranilic acid (CAA) has been studied in acidic media at Pb/PbO₂, boron-doped diamond (Si/BDD) and Ti/IrO₂ electrodes by bulk electrolysis experiments under galvanostatic control. The obtained results have clearly shown that the electrode material is an important parameter for the optimization of such processes, deciding of their mechanism and of the oxidation products. It has been observed that the oxidation of CAA generates several intermediates eventually leading to its complete mineralization. Different current efficiencies were obtained at Pb/PbO₂ and BDD, depending on the applied current density in the range from 6.3 to 50 mA cm⁻². Also the effect of the temperature on Pb/PbO₂ and BDD electrodes was studied.UV spectrometric measurements were carried out at all anodic materials, with applied current density of 25 and 50 mA cm⁻². These results showed a faster CAA elimination at the BDD electrode. Finally, a mechanism for the electrochemical oxidation of CAA has been proposed according to the results obtained with the HPLC technique.     

Anodic oxidation of azo dye C.I. Acid Red 73 by the yttrium-doped Ti/SnO2-Sb electrodes

This work was conducted to study the ability of anodic oxidation of azo dye C.I. Acid Red 73 (AR73) using the yttrium-doped Ti/SnO₂-Sb electrodes. The effects of Sb doping level, yttrium doping level, thermal decomposition temperature and cycle times of dip-coating thermal decomposition on the properties of the electrodes were investigated. The results showed that the excellent electrochemical activity of Ti/SnO₂-Sb-Y electrode can be achieved at a 7∶1 molar ratio of Sn∶Sb and thermal decomposition temperature of 550°C. Moreover when the cycle times of dip-coating and thermal decomposition were up to 10 times, the performance of the electrode tends to be stable. The Ti/SnO₂-Sb electrodes doped with yttrium (0.5 mol-%) showed the most excellent electrochemical activity. In addition, the influences of operating variables, including current density, initial pH, dye concentration and support electrolyte, on the colour removal, chemical oxygen demand (COD) removal and current efficiency were also investigated. Our results confirmed that the current efficiency increased with the concentrations of dye and sodium chloride. Moreover, increasing the current density and the initial pH would reduce the current efficiency.     

新型钛基体PbO2电极的制备及降解性能研究

采用电沉积法制备钛基体PbO2电极并对其表面形貌进行了表征,所制备的电极具有较高的析氧电位和良好的电催化活性。以制备的钛基PbO2为阳极,抛光钛电极为阴极,分别进行电流密度、反应时间、pH、电解质质量浓度等单因素试验,确定PbO2电极对亚甲基蓝的最优降解条件为:pH=6,电解质质量浓度为5.0 g.L-1,电流密度为5×10-2A.cm-2,该条件下亚甲基蓝1 h的降解率可以达到99%;且电流密度为0.25×10-2A.cm-2时能耗最低。     

Electrochemical oxidation of aniline at boron-doped diamond electrodes

The electrochemical oxidation of aniline at boron-doped diamond (BDD) electrodes was investigated by cyclic voltammetry, steady-state polarization measurements and bulk electrolysis under potentiostatic control. It was found that acidic media is suitable for efficient electrochemical oxidation of aniline, because at low pH, the potential required for avoiding electrode fouling is lower than in neutral and alkaline media. The results of the longtime polarization measurements suggested that more anodic potentials ensure slightly higher efficiency for the conversion of aniline to CO₂, while the direct oxidation process does not play a prominent part in the overall electrochemical incineration of aniline. The current efficiencies (44%) and the efficiency of aniline conversion to CO₂ (80%) favourably compare with those reported for other electrochemical methods for aniline destruction. The results demonstrate the possibility of using BDD as an electrode material for electrochemical wastewater treatment, mainly when very high anodic potentials are required.