紫外光协助下DSA电极对1,4-苯醌的强化开环作用研究

以商品化DSA电极为光电极,以1,4-苯醌为模型污染物进行了光电催化降解,考察了外加电解质、外加电场强度和初始pH条件等因素的影响.结果表明,光电催化氧化过程的TOC去除率是单独光催化氧化和电催化氧化过程之和的1.25倍,光电催化降解过程具有更高的降解效率,证明光催化氧化和电催化氧化过程的耦合产生了一定的协同作用.外加电解质和外加电场均能在一定浓度和强度范围内有效提高光电催化降解效率.酸性和中性pH条件利于1,4-苯醌的开环矿化.探讨了光电催化氧化机制,指出以电化学氧化作用为主导的光助电催化氧化过程能够高效产生羟基自由基,降解效率可调,在水处理中更具实用价值.     

金刚石膜电极电化学氧化提高废水可生化性的研究

采用掺硼金刚石膜电极(BDD)电化学氧化的方法提高2-氯苯酚废水的可生化性,与钛基钌铱氧化物电极(DSA)进行对比,研究了该方法的机理.结果表明,BDD电极电化学氧化2.0h后,BOD5/CODCr值达到0.42,有效提高了废水的可生化性,而DSA电极电化学氧化2.0h后,BOD5/CODCr值仅为0.24.机理研究表明,由于BDD电极具有高的析氧电位,可产生大量的羟基自由基(×OH),能够使2-氯苯酚的苯环充分开环,形成草酸、顺丁烯二酸等易生化处理的中间产物,从而使可生化性提高;而DSA电极的析氧电位较低,产生羟基自由基的能力较差,不能有效地提高废水的可生化性.     

三维电极处理氨氮废水的电化学反应特性

采用无短路电流的电极粒子串作为三维电极的填充材料,以更好地揭示其电化学反应特性.研究证实在电化学反应过程中涉及到两个阶段,80min前氨氮的去除机理主要是与在粒子电极阴极端产生的羟基自由基发生电氧化反应,80min后少量的中归反应起到协同作用,从而达到更佳的去除效果.实验结果还说明随着槽电压的增大,氨氮去除率不断增大;当电压为25V,pH值为10的情况下得到较大的去除率.     

Electrically enhanced photodegradation of an azodye(Acid Orange II) using a Pt/TiO_2 film electrode irradiating with an UV lamp

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Electrically enhanced photodegradation of an azodye(Acid Orange Ⅱ) using a Pt/TiO2 film electrode irradiating with an UV lamp

A photoelectrochemical process in the degradation of an azodye(Acid Orange II)on a Pt/TiO2 film electrode was investigated.By using the glass device and the voltage stabilized source of direct current,decolorization ratios higher than 78% were observed during a period of 5h.Comparing this value with the sum of the decolorization ratios obtained by a sole application of electrochemical(lower than 3%)and photochemical(about 23%)procedures, a significant synergic effect between both processes was observed.The effects of adscititious voltage and pH value on the decolorization ratios were obvious while the effect of the amount of aeration was minor.     

Mechanism of enhanced removal of quinonic intermediates during electrochemical oxidation of Orange Ⅱ under ultraviolet irradiation

The effect of ultraviolet irradiation on generation of radicals and formation of intermediates was investigated in electrochemical oxidation of the azo-dye Orange I1 using a TiO2-modified β- PbO2 electrode. It was found that a characteristic absorbance of quinonic compounds at 255 nm, which is responsible for the rate-determining step during aromatics degradation, was formed only in electrocatalytic oxidation. The dye can be oxidized by either HO radicals or direct electron transfer. Quinonic compounds were produced concurrently. The removal of TOC by photo-assisted electrocatalytic oxidation was 1.56 times that of the sum of the other two processes, indicating a significant synergetic effect. In addition, once the ultraviolet irradiation was introduced into the process of electrocatalytic oxidation, the degradation rate of quinonic compounds was enhanced by as much as a factor of two. The more efficient generation of HO radicals resulted from the introduction of ultraviolet irradiation in electrocatalytic oxidation led to the significant synergetic effect as well as the inhibiting effect on the accumulation of quinonic compounds.     

pH值对氨氮电化学氧化产物与氧化途径的影响

摘要:研究了含氨氮废水在循环流动式电解槽中的电化学氧化,讨论了pH值对氨氮电化学氧化效果、产物及其途径的影响。结果表明,在弱碱性条件下,有利于电解过程中羟基自由基和游离氯的生成,氨氮的电化学氧化速率较大。在有氯离子存在的情况下,氨氮电化学氧化过程中有氯胺生成,氯胺的组成与体系的pH值有关,当pH>9时,一氯胺占优势;当pH=7时,一氯胺和二氯胺同时存在,并且近似相等;当pH<5时,主要是二氯胺;pH值大于5时,可以避免三氯化氮的生成。在电流密度为20mA/cm2时,电解产生的羟基自由基小于5×10-15mol/L,氨氮电化学氧化的2种途径中间接氧化起主要作用。     

pH值对氨氮电化学氧化产物与氧化途径的影响

研究了含氨氮废水在循环流动式电解槽中的电化学氧化.讨论了pH值对氨氮电化学氧化效果、产物及其途径的影响.结果表明,在弱碱性条件下.有利于电解过程中羟基自由基和游离氯的生成.氨氮的电化学氧化速率较大.在有氯离子存在的情况下,氨氮电化学氧化过程中有氯胺生成,氯胺的组成与体系的pH值有关.当pH>9时,一氯胺占优势;当pH=7时.一氯胺和二氯胺同时存在,并且近似相等;当pH<5时,主要是二氯胺;pH值>5时,可以避免三氯化氮的生成.在电流密度为20mA/cm2时.电解产生的羟基自由基<5×10-15mol/L,氨氮电化学氧化的2种途径中间接氧化起主要作用.     

Preparation of TiO_2/Ti mesh photoelectrode and properties

ＩｎｔｒｏｄｕｃｔｉｏｎＭｕｃｈｉｎｖｅｓｔｉｇａｔｉｏｎｓｓｈｏｗｅｄｔｈａｔｐｈｏｔｏｃａｔａｌｙｔｉｃｏｘｉｄａｔｉｏｎｏｆＴｉＯ2 ｐｒｏｖｉｄｅｓａｎｅｆｆｅｃｔｉｖｅｔｅｃｈｎｏｌｏｇｉｃａｌｍｅｔｈｏｄｆｏｒｔｈｅｄｅｇｒａｄａｔｉｏｎｏｆｔｈｅｏｒｇａｎｉｃｃｏｎｔａｍｉｎａｎｔｓｉｎｗａｔｅｒ(Ａｎｄｊｅｌｋａ ,2 0 0 0 ;Ｆｕｊｉｓｈｉｍａ ,1972 ;Ｈｉｄａｋａ ,1992 ;Ｋｅｓｓｅｌｍａｎ ,1997) .Ｉｎｏｒｄｅｒｔｏｏｖｅｒｃｏｍｅｔｈｅｓｈｏｒｔｃｏｍｉｎｇｓｔｈａｔｔｈｅｒｅｃｏｖ…     

Preparation of TiO2/Ti mesh photoelectrode and properties

An innovative photoelectrode,TiO2/Ti mesh electrode,was prepared by anodisation.In anodisation,0.5 mol/L H2SO4 was used as electrolytic solution,the current had been constantly 1A from the beginning of the oxidation until reaching a designed voltage.Results showed that the photocatalytic activity of electrode was better when the designed voltage was 160 V.The morphology and the crystalline texture of the TiO2 film on mesh electrode were examined by scanning electronic microseopy and Raman spectruscopy respectively.The examination results indicated that the structure and properties of the film depended on anodisation rate,and the anatase was the dominant component under the eontrolled experimental conditions.Degradation of Rhodamine B in photocatalytic (PC)and photoelectrocatalytic(PEC) reaction was investigated.     

电化学氧化除氨氮过程中羟基自由基及中间产物定量分析

采用高效液相色谱对电化学氧化除氨氮过程,不同电流密度,Cl-浓度及初始pH值的·OH进行定量检测和分析,同时,对不同初始pH值和电流密度下,电化学氧化除氨氮的中间产物进行了定量分析,结果表明:·OH产生量与电流密度成正比,当有Cl-存在,且在碱性条件下会抑制·OH的产生;初始pH值为偏碱性时,NO2-和氯胺的产量均有所增加.建议电化学氧化脱氨氮过程,尽量保持溶液pH值在中性或酸性条件下;电流密度对氨氮电化学氧化过程中各中间产物的量有着较大影响,在电流密度为10mA/cm2时,活性物质产量最高,且有害中间产物产量最低.     

金刚石膜电极对有机污染物的电催化特性

研究了化学气相沉积法(CVD)制备得到的掺硼金刚石膜电极的物理性质和电化学性能.用扫描电子显微镜(SEM)法表征了金刚石膜的表面微观结构,采用循环伏安法和交流阻抗法研究了电极的电化学性质.结果表明,金刚石薄膜表面形态为复晶结构,颗粒大小均匀,掺硼后使电极具有良好的导电性能.金刚石膜电极具有很宽的电势窗口,在酸性、中性和碱性3种介质中分别为4.3V、4.0V和3.0V.同时,金刚石膜电极的背景电流非常低,为-9×10^-6～5×10^-7A.在铁氰化钾电解液中,金刚石膜电极表面在反应过程中始终保持良好的活性,在表面进行的电化学反应具有良好的准可逆性,其电极动力学主要是受扩散过程所控制.金刚石膜电极对有机污染物的催化氧化作用具有选择性.与铂电极和石墨电极相比,金刚石膜电极对苯酚、硝基苯等芳香化合物的催化氧化强烈,氧化过程较为简单、彻底.这些性质表明金刚石膜电极是一种非常适用于环保处理的新型电极.     

CuO-CeO2/γ-Al2O3粒子电极对垃圾渗滤液降解特性

研制了负载型CuO-CeO2/γ-Al2O3粒子电极,并与活性炭颗粒混合填充于主阴阳极之间,实现三维电催化氧化反应,采用XRD、SEM对粒子电极进行表征.结果表明, CuO-CeO2/γ-Al2O3粒子电极对垃圾渗滤液显示了良好的电催化活性和稳定性,在pH为7.0、槽电压10V、空气流速0.04m3·h-1反应条件下,150min后, COD、氨氮去除率达到87.8%、45.4%,去除效果较传统二维平板、三维复极性电解槽更高,经20次反复使用后仍具有一定催化活性.研究了电-多相催化氧化体系对垃圾渗滤液降解的动力学规律,表明渗滤液降解符合准一级反应动力学规律;并在此条件下,体系以直接氧化占优.     

电增强零价铁强化厌氧氨氧化处理高氮养猪废水

为解决ZVI(零价铁)电极表面的钝化问题,实现anammox(厌氧氨氧化)工艺稳定、高效地运行,采用EEZVI-UASB(电增强零价铁-升流式厌氧污泥床)技术处理养猪废水,研究了EEZVI电极电压、ρ(COD_Cr)及脱氮贡献率的相关性. 结果表明,在温度为(35±1)℃、pH为6.80～7.10、电极电压为0.60 V的条件下,EEZVI-UASB对NH₄+-N和NO₂--N的去除率均维持在较高的水平;NH₄+-N去除率＞90.00%,NO₂--N去除率＞96.00%,TN平均去除率>90.00%. 当EEZVI电极电压为0.60 V时,AAOB(厌氧氨氧化菌)的活性为91.10 mg/(g·d)(以NH₄+-N计);EEZVI-UASB中的优势功能菌主要为Pseudomonas属,其菌属16S rDNA的PCR扩增相似性达97%;系统中同时存在着反硝化、anammox、甲烷化等反应;其中anammox占主导作用,其对TN去除率的贡献率为54.10%~93.30%,反硝化及其他反应对TN去除率的贡献率为6.70%~45.90%.      

TiO2薄膜光催化体系中羟基自由基的水杨酸分子探针法测定

以水杨酸为分子探针物,以分光光度法测定了纳米TiO2薄膜光催化体系中产生的羟基自由基(·OH).结果表明,水杨酸的自然氧化程度较低,可以作为分子探针测定·OH的产生;实验中最佳的光照时间为60min;水杨酸浓度对·OH的测定影响较大,其最佳值为50 mg·L-1;pH值对·OH的测定影响较大,最佳值为6;最佳实验条件下,分析得到·OH的稳态浓度为1.68×10-14 mol·L-1.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

Activated carbon enhanced ozonation of oxalate attributed to HO. oxidation in bulk solution and surface oxidation： Effect of activated carbon dosage and pH

Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.     

Determination of hydroxyl radicals in TiO2/Ti photoelectrocatalytic oxidation system using Fe(phen)3 2+ spectrophotometry

A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic(PEC)oxidation system was established by o-phenanthroline-Fe(Ⅱ)(Fe(phen)32+) spectrophotometry and using anion exchange membrane. Fe concentration of hydroxyl radicals can be calculated through determining the change of the Fe(phen)33+ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 (isoelectric point), and the change direction of pH after illumination tended to nearby isoelectric point.     

粒子电极对苯酚废水的电催化降解

以溶胶-凝胶法制备了负载型复合金属氧化物Mn-Sn-Sb/γ-Al₂O₃粒子电极,用该粒子电极取代平板电极,对苯酚水溶液进行了电催化降解的研究,并考察了pH,电解质浓度,槽电压,进水ρ(苯酚),反应温度和气体流量等因素对苯酚去除率的影响.结果表明,当反应温度为25 ℃,pH为6.4,气体流量为0.5 L/min,槽电压为6.5 V,电解质浓度为0.025 mol/L时,电催化降解质量浓度为200 mg/L的苯酚水溶液150 min,苯酚去除率为94.0%,催化活性较高.提高进水ρ(苯酚),会使反应表现为自抑制作用;提高温度有利于苯酚电催化氧化的进行,但会增加石墨电极损耗和催化剂溶出量,因此在选择电催化氧化温度时要考虑设备的耐蚀性和电极的稳定性.      

铟掺杂PbO2电极制备及电催化降解强力霉素

采用电沉积技术制备了铟掺杂PbO₂电极 （In-PbO₂）. 利用扫描电子显微镜 （SEM）、X射线衍射 （XRD）、循环伏安 （CV）、极化曲线 （LSV）、强化寿命试验和荧光光谱分析了铟掺杂对电极物理、电化学性能的影响,并考察了铟掺杂PbO₂电极对强力霉素模拟废水的电催化降解能力.结果表明,与未掺杂PbO₂电极相比, In掺杂后PbO₂电极表面更加平整致密,裂纹数量减少,晶粒明显细化,比表面积增加,产生羟基自由基的能力增强.当掺杂量为2g/L,制备的电极电化学性能最高,析氧电位最高（1.73V）,电极强化寿命从84h提高到148h.电解150min后,强力霉素降解率、TOC去除率、矿化电流效率（MCE）分别为98.2%、30.4%和3.01%,优于未掺杂PbO₂电极（90.1%、26.4 %、2.63%）.