BDD和PbO2电极电化学氧化苯并三氮唑的对比研究

分别构建了以掺硼金刚石膜电极(BDD)和二氧化铅电极(Pb O2)为阳极的电化学体系,对比考察了两种电极对难降解有机污染物苯并三氮唑(BTA)的降解及体系的矿化效果,并从电极产生羟基自由基(·OH)的数量与形态角度深入探讨了影响电极矿化能力大小的内在因素.结果表明:1BDD和Pb O2电极均对BTA有较好的降解效果,电解12 h后BTA去除率分别为99.48%和98.36%,但BDD电极的矿化能力明显强于Pb O2电极,电解12 h后矿化率分别为87.69%和35.96%;2BDD体系阳极·OH产生速率和阴极H2产生速率均低于Pb O2体系,即表面活性位点数量少于Pb O2电极,因此·OH数量不是决定矿化能力大小的关键;3BDD电极表面吸附氧活性更强,结合能(532.37e V)大于Pb O2(530.74e V),且表面吸附层更薄,产生的·OH形态更自由,是决定其具有更大矿化能力的关键因素.     

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate (DMP) up to 125 mg/L with sodium sulfate (Na2SO4) as supporting electrolyte within the pH range 2.0–10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond (BDD) as anode. Electrolyses were carried out at constant current density (1.5–4.5 mA/cm2). Complete mineralization was always achieved owing to the great concentration of hydroxyl radical (.OH) generated at the BDD surface. The e ects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current e ciency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography (HPLC) revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry (GC-MS) and a general pathway for the electrochemical incineration of DMP on BDD was proposed.     

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.     

电流密度对BDD电极电化学矿化吲哚的影响与机制

掺硼金刚石膜(BDD)电极电化学氧化法是去除难降解有机污染物的有效手段.与总有机碳(TOC)等的测定相比,气态中间产物的逸出量能够更直观有效地反映有机物的矿化程度与去除效果.本研究以吲哚为代表性污染物,通过对比不同电流密度(10、20和30 m A·cm-2)下BDD电极对吲哚的去除率与矿化率,结合降解过程中碳和氮形态的变化与守恒情况,分析吲哚的降解机制.结果表明,BDD电极对吲哚有良好的去除效果,电流密度为10、20、30 m A·cm-2时,吲哚达到100%去除的时间分别为8、5和4 h;TOC去除率、CO_2产生量均随电流密度的增加而增大,证明矿化率与电流密度成正相关;电解产生的CO_2气体与TOC、无机碳(TIC)构成了碳守恒体系.4~5 h时,体系TOC、TON和CO_2产生量均没有变化,表明电解产生的靛红具有较高的稳定性,此时为中间产物积累阶段;XPS表征进一步证实了中间产物靛红、苯醌等在电极表面的吸附,随着电解时间的延长,这些吸附的中间产物可进一步被降解.本研究从气态产物检测及碳氮形态分析与守恒的角度阐释吲哚矿化过程,对于辅助揭示有机物的电解过程有重要意义.     

Enhanced photoelectrocatalytic degradation of ammonia by in situ photoelectrogenerated active chlorine on TiO2 nanotube electrodes

TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.     

真空紫外/氯处理饮用水典型致嗅物质

为有效去除常规水处理工艺难以去除的典型致嗅物质二甲基异莰醇（2-MIB）和土臭素（GSM）,采用真空紫外/氯高级氧化技术,探讨该技术降解致嗅物质的效能,研究在不同紫外光强、氯浓度、pH、重碳酸盐浓度、腐殖酸浓度条件下致嗅物质的降解效果,分析羟基自由基在致嗅物质降解中起到的作用,目标物浓度采用吹扫捕集-气质联用法（GC/MS）测定.结果表明,真空紫外/氯高级氧化技术可以有效去除饮用水典型致嗅物质,相比紫外/氯高级氧化技术而言,在30 min内2-MIB和GSM的去除率分别提高15%和8%;随着氯浓度和紫外光强度的增加,致嗅物质的降解速率加快;在弱酸性条件下,致嗅物质的去除效果明显,在pH为5时,2-MIB和GSM的去除率在反应10 min后分别可以达到95%和96%;水体中重碳酸盐和腐殖酸的存在,竞争消耗反应体系中的自由基,对致嗅物质的降解起到抑制作用;在反应体系中投加1 mmol·L^-1羟基自由基抑制剂叔丁醇后,2-MIB和GSM的去除率下降明显,分别下降40%和31%,表明羟基自由基在致嗅物质的去除中起到主要作用.     

声电氧化处理扑热息痛的研究

采用电沉积法制备了新型稀土和氟树脂共掺杂二氧化铅电极,并用于声电氧化体系处理扑热息痛(APAP)废水.结果表明,采用稀土掺杂电极后,APAP的去除效率及矿化效率大幅度增加,显示出催化效率的显著提升.工艺因素作用规律结果表明,Ce-PTFE共掺杂PbO2电极在电解质14.2 g.L-1、功率为49.58 W.cm-2、频率50 Hz、pH为3、电流密度为71.43 mA.cm-2的条件下去除APAP效果最佳.反应进行2 h后,500 mg.L-1APAP去除率为92.20%,COD和TOC的去除率分别为79.95%和58.04%,电流效率高达45.83%.结合GC-MS、HPLC、IC等分析手段,检测到了主要中间产物包括苯醌,苯甲酸、乙酸、顺丁烯二酸,乙二酸、甲酸等,推测了APAP的可能降解途径.     

电化学氧化PFOA阳极材料筛选及其机制研究

全氟辛酸(PFOA)具有环境持久性及内分泌干扰性,传统的生物降解及高级氧化法对PFOA的去除效果微弱.本研究采用电化学氧化法降解PFOA,选取BDD(掺硼金刚石电极)、Pt、Ti、Ti/RuO2、Ti/RuO2-IrO2、Ti/In2O3、Ti/SnO2-Sb2O5-IrO2、Ti/SnO2-Sb2O5-RhO2、Ti/SnO2-Sb2O5、Ti/SnO2-Sb2O5-CeO2和Ti/SnO2-Sb2O5-Bi2O3这11种阳极材料为备选电极.采用线性扫描伏安法测试析氧电位(OEP),评价11种电极对PFOA的降解效果和脱氟效果,并采用超声-电化学协同方法间接证明PFOA分子在电极表面的直接电子转移是降解反应的第一步.Ti/SnO2-Sb2O5-Bi2O3、Ti/SnO2-Sb2O5-CeO2、Ti/SnO2-Sb2O5和BDD对PFOA有较好的电氧化效果,降解率分别是89.8%、89.8%、93.3%和98.0%.Pt、Ti/SnO2-Sb2O5-RhO2、Ti/SnO2-Sb2O5-IrO2和Ti/In2O3对PFOA的电氧化效果微弱,降解率分别是2.1%、2.3%、12.5%和3.1%.而Ti、Ti/RuO2和Ti/RuO2-IrO2对PFOA没有电氧化能力.PFOA分子经过电极表面的直接电化学氧化发生脱羧反应,后经过逐步脱掉CF2单元的循环生成短链的全氟羧酸类化合物C6F13COO-、C5F11COO-、C4F9COO-和C3F7COO-.     

Research on the degradation mechanism of pyridine in drinking water by dielectric barrier discharge

Pyridine, an important chemical raw material, is widely used in industry, for example in textiles,leather, printing, dyeing, etc. In this research, a dielectric barrier discharge(DBD) system was developed to remove pyridine, as a representative type of nitrogen heterocyclic compound in drinking water. First, the influence of the active species inhibitors tertiary butanol alcohol(TBA),HCO_3~-, and CO_3~(2-)on the degradation rate of pyridine was investigated to verify the existence of active species produced by the strong ionization discharge in the system. The intermediate and final products generated in the degradation process of pyridine were confirmed and analyzed through a series of analytical techniques, including liquid chromatography–mass spectrometry(LC–MS), high performance liquid chromatography(HPLC), ion chromatography(IC), total organic carbon(TOC) analysis, ultraviolet(UV) spectroscopy, etc. The results showed that the degradation of pyridine was mainly due to the strong oxidizing power of ozone and hydroxyl radical produced by the DBD system. Several intermediate products including 3-hydroxyl pyridine, fumaric acid, 2, 3-dihydroxypyridine, and oxalic acid were detected. Nitrogen was removed from the pyridine molecule to form nitrate. Through analysis of the degradation mechanism of pyridine, the oxidation pathway was deduced. The study provided a theoretical and experimental basis for the application of DBD strong ionization discharge in treatment of nitrogen heterocyclic compounds in drinking water.     

腐殖酸在氯离子体系中的电解氧化特性

通过小型实验对腐殖酸模拟废水进行了电解氧化处理,考察了阳极材料、氯离子初始浓度对腐殖酸电解氧化处理效果的影响,探讨了腐殖酸在电解处理过程中分子量分布的变化及电解产生的低分子量产物组成.研究结果表明,PbO2阳极的电解处理效果比 Ru-Ir/Ti阳极的处理效果好,当废水在氯离子体系中电解时.可缩小2种阳极对CODCr去除效果的差距;电解后溶液中溶解性有机物的分子量分布向小分子量方向转变;当溶液中有氯离子存在时,电解过程产生的 ClO-的间接氧化作用可有效地将大分子有机物降解为小分子有机物.腐殖酸在氯离子体系中电解生成的低分子量化合物主要有 CO2、氯仿、乙酸、苯酚、苯乙醇、2H-1,4 氯苯基双氮杂卓-2-1,1-(1,1-二甲基乙基)-萘酚、3-(3-羧基-4-羟基-5-硝基酚)-D-丙氨酸等.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

超声强化金刚石膜电极电化学降解效率的机制

从电化学氧化的传质过程、吸附与脱附、电极反应3个步骤,考察了超声强化金刚石膜电极(BDD)电化学降解效率的机制.超声对上述3个步骤都有显著影响.超声增强了污染物的传质过程,苯酚和邻苯二甲酸的传质系数分别由5.4×10-6m/s和6.7×10-6m/s增大至2.0×10-5m/s,提高了270%和199%.污染物在BDD电极表面的电化学吸附特性决定了超声对吸附与脱附过程的作用.苯酚的吸附量大,但中间产物难于脱附,超声虽然使得吸附量由6.49×10-10mol/cm2减小至1.39x10-10mol/cm2,但促进了产物的脱附,产生了正效应,有利于直接氧化,氧化峰电流提高了32%;邻苯二甲酸的吸附能力弱,超声使得吸附量由1.25×10-11mol/cm2进一步减小至3.11×10-12mol/cm2,产生了负效应,导致直接氧化消失.超声可以显著提高BDD电极的降解效率,而且对苯酚降解的促进作用更为明显.苯酚的平均电化学氧化能量利用率提高了287%,高于邻苯二甲酸的224%,这主要是因为超声可以同时强化苯酚的直接氧化和间接氧化,但对于邻苯二甲酸,间接氧化得到了加强,却不发生直接氧化.     

掺硼金刚石电极处理榨菜废水试验研究

掺硼金刚石(BDD)电极在电化学氧化难生物降解性废水时具有电化学性能良好、处理效果好等特点,因而受到广泛关注.本试验采用BDD电极电化学氧化榨菜废水,并考察了稀释比、初始pH值、电流密度、极板间距等参数对COD、氨氮(NH3-N)去除率的影响.试验结果表明:在稀释比为1∶2、电流密度50 mA·cm-2、未调节pH值、极板间距为15 mm的最优工况下,COD、NH3-N去除率分别为96.9%、100%.COD去除率满足线性方程y=0.435t(R2=0.9899),NH3-N去除率满足多项式拟合方程y=0.53+0.936t+0.031t2-3.46×10-4t3(R2=0.9956).研究表明,BDD电极电化学氧化榨菜废水是一种有效的高级氧化工艺.     

The roles of active species in photo-decomposition of organic compounds by microwave powered electrodeless discharge lamps

Knowledge of the effective radiation spectrum irradiating substrates from microwave powered electrodeless discharge lamps(MEDLs), and the active species that directly oxidize substrates in the photolytic process, is fragmentary and unclear. In this work, we conducted a comparative study using MEDLs made with quartz envelopes(MEDL-quartz) and with borosilicate Pyrex envelopes(MEDL-Pyrex) targeting the degradation of Rhodamine B(Rh B)via radical-extinguishing tests. We found that UVC/UVB radiation is essential to generate·OH and H2O2 in the MEDL-quartz system. The degradation of Rh B mostly originates from·OH species, which account for a contribution of 53.8%, while the remaining contribution is attributed to oxidation by H2O2 and direct photolysis. This degradation is influenced by several parameters. Acidic and neutral p Hs, but not extreme alkaline p H, benefit the degradation. To ensure a high intensity of UVC/UVB, the optimum ratio of the MEDL volume to the aqueous solution volume(VL/VS) is 0.4. Concentrations of 0.15–0.20 mmol/L of Rh B are suitable to obtain an effective quantum absorbance in the MEDL-quartz system,showing a high decomposition rate of 5.6 × 10-3(mmol/L)min-1. Moreover, two other substrates, Reactive Brilliant Red X-3B and Safranine T, were tested and found to be efficiently degraded in the MEDL-quartz system.     

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...     

Enhancement of municipal sludge dewaterability by electrochemical pretreatment

Electrolysis is a promising technology to improve sludge dewaterability efficiently with negligible environmental impact. To intensify the electrolytic efficiency, the effect of electrolytes (NaCl, Na₂SO₄, NaNO₃, and NaClO₄) on electrolysis pretreatment of municipal sludge and its mechanisms was investigated using Ti/PbO₂ electrodes. The electrolytes, which enhanced the production of oxidative radicals, showed a significant synergetic effect in reducing the capillary suction time (CST) of sludge. NaCl was distinguished from the other electrolytes since it formed a large amount of active chlorine species, which oxidized the sludge cells to improve the sludge dewaterability. The surface morphologies as well as the soluble proteins and polysaccharides were analyzed to unravel the underlying mechanisms of sludge dewaterability. Additionally, an economic assessment showed that NaCl addition in the electrolysis pretreatment can be a suitable technique for enhancing municipal sludge dewaterability.     

Feasibility of bioleaching combined with Fenton oxidation to improve sewage sludge dewaterability

A novel joint method of bioleaching with Fenton oxidation was applied to condition sewage sludge. The specific resistance to filtration (SRF) and moisture of sludge cake (MSC) were adopted to evaluate the improvement of sludge dewaterability. After 2-day bioleaching, the sludge pH dropped to about 2.5 which satisfied the acidic condition for Fenton oxidation. Meanwhile, the SRF declined from 6.45 × 10¹⁰ to 2.07 × 10¹⁰ s²/g, and MSC decreased from 91.42% to 87.66%. The bioleached sludge was further conditioned with Fenton oxidation. From an economical point of view, the optimal dosages of H₂O₂ and Fe^2 + were 0.12 and 0.036 mol/L, respectively, and the optimal reaction time was 60 min. Under optimal conditions, SRF, volatile solids reduction, and MSC were 3.43 × 10⁸ s²/g, 36.93%, and 79.58%, respectively. The stability and settleability of sewage sludge were both improved significantly. Besides, the results indicated that bioleaching-Fenton oxidation was more efficient in dewatering the sewage sludge than traditional Fenton oxidation. The sludge conditioning mechanisms by bioleaching-Fenton oxidation might mainly include the flocculation effects and the releases of extracellular polymeric substances–bound water and intercellular water.     

Effects of metal ions on the catalytic degradation of dicofol by cellulase

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, K_m, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, V_max, was 0.40 mg/L/min, while that of free cellulase was K_m = 8.18 mg/L, and V_max = 0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn^2 +, reversible competition with Cd^2 +, and irreversible inhibition by Pb^2 +. Ca^2 + promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment.     

热活化过硫酸盐氧化降解水溶液中的抗生素卡巴多司和奥喹多司

硫酸根自由基(SO■)高级氧化技术(SR-AOPs)是一种新型的原位化学氧化技术(ISCO),在水处理领域具有广阔的应用前景,可用于治理土壤和地下水中抗生素污染.本研究采用热活化过硫酸盐(PS)产生SO■,考察其对水溶液中抗生素卡巴多司(CBX)和奥喹多司(OQX)的降解效果,评估操作参数和水质成分对CBX降解的影响,并对CBX的降解产物进行鉴定.结果表明,与OQX相比,CBX更容易被热活化PS工艺氧化降解,这可能是因为CBX含有富电子的腙支链,而OQX含有惰性的酰胺支链.升高温度、增加PS浓度和降低溶液pH值均可显著促进CBX的降解.HCO~-_3的存在对CBX降解有促进作用,可能是由于生成的碳酸根自由基(CO■)参与了反应.Suwannee河富里酸(SRFA)具有双重影响,低浓度时促进CBX降解,而高浓度时呈现抑制作用.NO~-_3的存在对CBX的降解没有明显影响,而NO~-_2的存在可以显著抑制其降解.CBX在天然地表水中的降解效率低于在地下水中的效率,可能与不同水质中天然有机质的含量有关.产物鉴定表明,热活化PS氧化降解CBX生成了羟基化、脱氧和支链断裂产物,表明氧化反应主要改变了CBX分子中的腙支链和N—O结构.研究表明,热活化PS工艺可有效降解水溶液中的CBX和OQX,但在该技术实际应用时应充分评估天然水质成分的影响.