酸性条件下黄铁矿氧化机制的研究

以黄铁矿粉末制备成的碳糊电极为工作电极,利用循环伏安曲线和极化曲线等电化学手段,对酸性条件下黄铁矿的氧化过程和机制进行了研究.结果表明,黄铁矿的氧化主要包括以下两个过程:首先,黄铁矿(FeS2)矿物晶格中的Fe2+溶出而被氧化为Fe3+,此过程会伴随有如硫单质、缺铁硫化物(Fe1-xS2)和多硫化物(FeSn)等氧化中间产物的生成,覆盖在黄铁矿的表面而形成一层钝化膜,阻碍了其氧化溶解过程;接着,黄铁矿表面的钝化膜被进一步氧化为可溶性的SO24-.在酸性条件下,黄铁矿氧化反应的最终产物为Fe3+和SO24-.另外,在所研究的酸度范围内,随着H2SO4溶液浓度的增大,体系的开路电位和腐蚀电位均正移,氧化和还原的峰电流值升高,腐蚀电流增大,说明增加体系的酸度会促进黄铁矿的氧化过程.     

纳米铂微粒电极催化氧化有机污染物的研究

采用电化学阴极还原-阳极氧化方法制备了纳米铂微粒电极.电极表面的微观结构表征表明,铂微粒在三维网状的氧化钛膜孔道中呈均匀、高度分散状态,且粒径细小,铂微粒充分裸露,使得纳米铂微粒电极活性点多,电催化性能高.采用循环伏安法研究了铂微粒电极对有机小分子代表性物质甲醇的电催化氧化行为.结果表明,在酸性、中性和碱性介质中纳米铂微粒电极对甲醇的电催化氧化性能均明显优于光滑铂片电极,甲醇在纳米铂微粒电极上产生的氧化电流密度比光滑铂片电极高100倍以上.2种铂电极催化氧化降解甲醇、苯酚和甲基橙3种有机物时,纳米铂微粒电极的平均氧化电流效率是光滑铂片电极的数倍,这进一步表明纳米铂微粒电极对有机污染物具有良好的催化氧化降解能力.     

黄铜矿在含铁酸性介质中氧化过程的电化学研究

以天然黄铜矿为研究对象,运用开路电位,循环伏安曲线,Tafel极化曲线和交流阻抗(EIS)等电化学手段,对在硫酸介质中三价铁离子对黄铜矿的氧化过程的电化学行为进行了研究.结果表明,黄铜矿在酸性介质中的氧化可能通过两步反应完成,第一步中电极表面形成了一层主要成分是含硫中间产物的钝化膜,第二步则是黄铜矿主体的氧化.Fe3+离子有助于黄铁矿的直接氧化,在黄铜矿的溶解过程中起到了重要作用.极化曲线测量的结果显示随着溶液中Fe3+离子浓度的增加,黄铜矿的极化电流也在增加,黄铜矿也更容易进入钝化阶段.同时,交流阻抗对Fe3+离子浓度改变的响应也很敏感.     

溶液pH及电流浓度对电化学法生成羟基自由基降解机制的影响

用电化学稳态极化曲线分析方法讨论了溶液pH值及电流浓度对染料降解脱色的影响.实验结果表明,pH值将影响着阴极反应的方向、电极电位与染料降解脱色的效果.在酸性溶液中有利于过氧化氢的生成,阴极电位较低,但不利于随后的絮凝步骤;在中性溶液中染料降解脱色的综合效果较好,COD_Cr去除率可达80%以上.文中还讨论了电流浓度对降解脱色效果的影响,当电解槽内电流浓度达0.5 A/L时可取得满意的效果,电流浓度太大时,体系将伴随着析出氢气等的副反应,降解反应的电流效率下降.      

Photoelectrocatalytic degradation of high COD dipterex pesticide by using TiO2/Ni photo electrode

A TiO₂ thin film electrode deposited on porous nickel net (TiO₂/Ni) was prepared by the sol-gel method, and the surface morphology, crystal structure features and the grain size were characterized by Field emission scan electron microscopy (FESEM) and X-ray diffraction (XRD). The photoelectrocatalytic system was set up using a UV high-pressure mercury lamp as the light source, TiO₂ coated on foamed nickel as photo anode, Pt sheet as counter electrode and the pesticide dipterex in synthetic wastewater. Various factors that influence the photoelectrocatalytic decomposition of dipterex pesticide have been studied, such as degradation time, the type of electrolyte, current density, original pH value and different degradation methods. The prepared catalysts were employed to photoelectrocatalytically degrade the pesticide dipterex under UV irradiation, comparing the results with photocatalytic degradation and electrochemical oxidation. The results indicated that under the optimal conditions of 0.02 mol/L NaCl as the supporting electrolyte, current density = 2.5 mA/cm², pH 6.0 and dipterex pesticide 40 mg/L, and reaction time 2 hr, dipterex chemical oxygen demand (COD) removal rate and organophosphorous conversion of up to 82.6% and 83.5% were achieved, respectively. The method of photoelectrocatalytic degradation is more efficient than photocatalysis and electrochemical oxidation. The possible roles of the electrolytes on the reactions and probable mechanisms were also discussed.     

双极电化学氧化降解水中苯胺

采用钛基氧化物涂层材料（Ti/SnO2-Sb2O5）为阳极,石墨为阴极,在含Fe2＋和不含Fe2＋2种电解质条件下研究了苯胺的电化学氧化降解效率和机制.结果表明,Ti/SnO2-Sb2O5阳极氧化降解有机物的电位约2.0 V±0.1 V,而石墨阴极还原O2生成H2 O2的优化电位为-0.65 V.H2 O2单独作用不能...     

有机污染物苯胺在催化电极上氧化降解的途径

采用循环伏安法和测定催化电极在不同介质中的阳极极化曲线得到析氧电位的方法,考察了有机污染物苯胺在催化电极上的电催化氧化行为.研究结果表明,苯胺在不同催化电极和反应介质中的电催化氧化降解途径可分为协同氧化降解和间接氧化降解2种模型.催化电极对有机污染物的电催化性能、电极的析氧电位大小以及处理体系的介质环境等多方面因素决定了电催化氧化的降解途径并将影响电化学降解的效率.      

异步周期换向电凝聚法处理活性艳蓝X-BR模拟染料废水及其机理研究

针对传统电凝聚法处理废水过程中易出现的电极表面钝化和极化而影响处理效果的现象,采用铝和铁板作为两极同步换向方法,通过周期性改变电流方向使电极钝化和极化现象得以减缓或消失,并实现两极均可溶,利用铝、铁系无机絮凝剂共存时可提高处理效果的特点,对活性艳蓝X-BR模拟染料废水进行处理;通过正交试验,获得了该方法的最佳处理条件.在此基础上,为避免金属铝成分在废水中出现剩余影响水质,采用异步周期换向方式加以改进,考察了铝、铁电极不同通电时间对处理效果的影响,并利用紫外-可见光分光光度法、高效液相色谱法、ICP法、高分辨质谱技术、激光粒度分析仪等手段对废水处理过程主导因素和污染物去除机理以及该方法对强化处理效果的作用机理进行了分析.研究表明,最佳条件下采用异步换向周期电凝聚法处理活性艳蓝X-BR模拟染料废水30 min可使模拟废水脱色率接近100%,COD去除率可达76%以上;处理过程中起主导作用的是电凝聚过程而非电氧化还原过程;除大部分染料分子被电凝聚气浮或沉降导致脱色外,其余的活性艳蓝X-BR染料分子在电解作用下首先断裂生成了1,4-二氨基蒽醌-2-磺酸根,之后1,4-二氨基蒽醌-2-磺酸根又被直接絮凝上浮或沉降,或者在氢离子作用下发生了加氢反应使双键消失而脱色,模拟废水脱色是上述作用的综合结果.采用改进后的异步周期换向电凝聚法可以使铝铁离子凝聚过程形成的絮体具有更为合理的粒度和结构特性,从而更易于被去除,因此处理效果略优于同步换向和定向电流电凝聚过程,且可以实现处理后废水中铝离子含量降低到无法检出,避免其在处理后的废水中出现剩余影响水质.     

钛基β-PbO2阳极催化性能及氧化机理研究

采用提拉法和电沉积法制作Ti／SnO2＋Sb2O3／β-PbO2阳极,通过SEM扫描、XRD分析和极化曲线测定表征具有良好结构和催化性能。利用该电极氧化靛红水溶液,表征Ti／SnO2＋Sb2O3／β-PbO2电极氧化机理,阳极氧化以[·OH]氧化有机物,次级氧化以阳极生成的活性相对差、寿命较长的H2O2,O3氧化有机物。Ti／SnO2＋Sb2O3／β-PbO2阳极氧化有机物是湿式氧化费用的30％～50％,具有广泛应用前景。     

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.     

Production and contribution of hydroxyl radicals between the DSA anode and water interface

Hydroxyl radicals play the key role during electrochemical oxidation and photoelectrochemical oxidation. The production and e ect of hydroxyl radicals on the interface between DSA anode and water was investigated by examining the quenching e ect of iso-propanol on Orange II decolorization. We observed that with an increase in electrode potential from 4 to 12 V across electrodes at pH 7.0, the contribution percentage of hydroxyl radicals increased dramatically. More OH radicals were produced in acidic and alkaline conditions than at neutral conditions. At electrode potential of 4 V, the contribution percentage of hydroxyl radicals was obviously higher at near neutral pH conditions, while removal e ciency of Orange II achieved was the lowest concurrently. Finally, for photocatalytic oxidation, electrochemical oxidation, and photoelectrochemical oxidation using the same DSA electrode, the e ect of hydroxyl radicals proved to be dominant in photocatalytic oxidation but the contribution of hydroxyl radicals was not dominant in electrochemical oxidation, which implies the necessity of UV irradiation for electrochemical oxidation during water treatment.     

铬掺杂TiO2液相沉积膜可见光下降解甲基橙研究

实验用液相沉积法制备铬掺杂改性的二氧化钛(Cr-TiO2)薄膜电极,并在可见光下利用制备的电极对甲基橙溶液(MO)进行光电降解实验研究.并对制备的薄膜进行光电流(I-t)、交流阻抗(EIS)和Mott-Schottky等电化学相关表征.当掺杂浓度为0.2％时,薄膜电极具有最好的光电催化活性.在以0.2％ Cr-TiO2...     

Photoelectrochemical performance of birnessite films and photoelectrocatalytic activity toward oxidation of phenol

Birnessite films on fluorine-doped tin oxide(FTO) coated glass were prepared by cathodic reduction of aqueous KMnO_4. The deposited birnessite films were characterized with X-ray diffraction, Raman spectroscopy, scanning electron microscopy and atomic force microscopy.The photoelectrochemical activity of birnessite films was investigated and a remarkable photocurrent in response to visible light was observed in the presence of phenol, resulting from localized manganese d–d transitions. Based on this result, the photoelectrocatalytic oxidation of phenol was investigated. Compared with phenol degradation by the electrochemical oxidation process or photocatalysis separately, a synergetic photoelectrocatalytic degradation effect was observed in the presence of the birnessite film coated FTO electrode.Photoelectrocatalytic degradation ratios were influenced by film thickness and initial phenol concentrations. Phenol degradation with the thinnest birnessite film and initial phenol concentration of 10 mg/L showed the highest efficiency of 91.4% after 8 hr. Meanwhile, the kinetics of phenol removal was fit well by the pseudofirst-order kinetic model.     

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.     

X70钢在碳酸氢钠溶液中的腐蚀行为研究

通过电化学试验方法对X70钢在NaHCO3溶液中的腐蚀行为进行了研究.实验结果表明,当NaHCO3质量分数低于0.10%时,极化曲线呈现阳极活化溶解过程,高于0.10%时阳极极化出现钝化过程,并且在-0.6 V(vs.SCE)左右出现了一个新的小电流峰.通过对交流阻抗谱分析发现,高频区均是由略偏离半圆的容抗弧组成,并且实部有所收缩.HCO3-的还原反应在阴极过程中起主要作用,整个过程受极化控制.X70钢在NaHCO3溶液中的腐蚀速度随着NaHCO3质量分数的增大而增大,在试验结束后,对试样表面的腐蚀形貌进行了观察,并利用XRD分析出腐蚀产物主要为FeO(OH)和Fe3O4.     

脉冲电化学氧化降解亚甲基蓝

为改善传统电化学氧化的缺陷,将脉冲式供电引入到电化学氧化中,利用Ti/PbO₂-PVDF电极,对亚甲基蓝（MB）模拟染料废水进行电化学氧化降解处理,分析初始浓度、脉冲电压、脉冲频率、占空比和NaCl浓度等因素对降解效果的影响.结果表明,当MB初始浓度为100mg/L,脉冲电压为5.5V,脉冲频率为1500Hz,占空比为50%,NaCl浓度为0.01mol/L时,降解效果最好.在相同条件下,比较脉冲与直流两种供电模式下的电化学氧化效果.结果表明脉冲模式下,90min内MB脱色率、COD去除率及电流效率分别为100%、94.5%和60.1%,均高于直流模式;脉冲模式下能耗为0.013kWh/gCOD,远小于直流模式的0.107kWh/gCOD.上述结果表明脉冲供电模式相比于直流供电模式具有明显优势.     

光电化学协同催化降解甲基橙的研究

以TiO2/Ti薄膜电极为阳极、石墨电极为阴极、饱和甘汞电极为参比电极,设计了一种新型的双槽光电化学协同催化反应器,考察了阴极电位、反应时间、电解质浓度、溶液pH值等因素对甲基橙降解效果的影响.结果表明,电解质浓度对甲基橙的降解脱色效果影响不明显,而阴极电位、溶液pH值和反应时间则影响显著;色度为200度的甲基橙溶液,在阴极电位(Ec)为-0.6V、阴极槽初始pH3.0和阳极槽初始pH5.6、反应90min的条件下,阴极槽和阳极槽中甲基橙的脱色率分别为98.3%和51.3%,与仅靠TiO2/Ti薄膜阳极对有机物进行催化降解的“双槽单效”光电催化反应器相比,对甲基橙的催化氧化降解效率显著提高.降解前后的紫外-可见吸收光谱的变化表明,该双槽光电化学协同催化反应器不但可以同时使阴、阳两槽中的甲基橙脱色,且其苯环结构也被降解和矿化.     

逆电渗析反应器降解模拟甲基橙染料废水实验

利用逆电渗析（RED）技术可实现"废热治理废水"的目的.为探究RED反应器对染料废水的降解效果,构建了由40对膜构成的RED反应器.以NaCl水溶液作为工作溶液,甲基橙模拟废水作为降解对象,考察了废水流率、Cl^-浓度、Fe²⁺浓度、pH值、曝气流率和输出电流对模拟废水脱色率及COD去除率的影响.结果表明,对于RED反应器阳极回路印染废水,废水流率对其脱色率影响不大,但Cl^-浓度对其脱色率和COD去除率影响较大.对于RED反应器阴极回路印染废水,废水流率、Fe²⁺浓度、pH值和曝气流率均对其脱色率和COD去除率产生影响.当阳极回路废水氯盐浓度为0.5 mol·L^-1,阴极回路废水pH=2、Fe²⁺浓度为0.1 mmol·L^-1、曝气流率为600 mL·min^-1,两回路模拟废水流率均为82 mL·min^-1实验条件下,输出电流为0.25 A时,处理20 min后,阳/阴极回路模拟废水脱色率分别为99.9%和91.71%;处理80 min后,阳/阴极回路模拟废水COD去除率分别可达到52%和62%.     

FePMo12催化电化学反应降解染料废水的研究

采用IR和XRD等方法对自制磷钼酸铁(FePMo12)杂多酸进行表征,表明杂多阴离子具有Keggin结构.将FePMo12负载于修饰后的4分子筛(4A)上制备FePMo12/APTES-4A催化剂填充于电化学反应器中,考察电化学氧化体系对酸性大红3R染料废水的脱色效果.结果表明,FePMo12/APTES-4A催化剂对酸性大红3R模拟废水具有良好的催化效果,当活性组分负载量为3%时,在pH为4,槽电压为22 V,曝气量为0.08 m3·h-1,极板间距为3.0 cm反应条件下,90 min后脱色率达到75.3%,COD和TOC去除率分别达到65.4%和46.0%.加入支持电解质Na2SO4和NaCl后,NaCl对电催化降解染料废水有促进作用,而Na2SO4的加入使得废水的脱色效率降低.采用可见-紫外光谱对反应过程中间产物进行分析,表明染料分子中的共轭体系已基本被破坏.