Ce-PbO2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为:初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

Ce-PbO_2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为：初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

CoFe_2O_4/TiO_2/鳞片石墨粒子电极光电催化降解罗丹明B

采用溶胶-凝胶法制成CoFe_2O_4/TiO_2/鳞片石墨粒子电极,用电子扫描电镜(SEM)、X-射线衍射仪(XRD)和X-射线光电子能谱仪(XPS)对该粒子电极的形貌、晶体结构和元素组成进行分析,并将其应用于罗丹明B(Rh B)的光电催化实验;考察电解质浓度、粒子电极投加量、电压、pH和初始浓度等因素对罗丹明B降解的影响,并研究了罗丹明B的光电催化降解动力学。结果表明:光催化和电化学联合作用时,产生协同作用;在电解质Na_2SO_4溶液浓度为0.03 mol·L~(-1),粒子电极投加量为6.67 g·L~(-1),外加电压为8 V,pH为3,反应时间为45 min时,浓度为15 mg·L~(-1)的罗丹明B的去除率达到97.6%;罗丹明B的光电催化降解反应符合假一级动力学模型。     

掺杂锰矿粉的PbO2复合电极的制备与应用

采用高压塑片法制备了纯PbO2电极及掺杂锰矿粉的PbO2复合电极,通过扫描电镜、加速寿命测试对电极性能进行了考察,并探讨了用PbO2复合电极对弱酸性桃红BS溶液进行的电催化降解机制和工艺条件.结果表明.PbO2复合电极的使用寿命是纯PbO2电极的3.3倍;在所考察的范围内,随着电流密度的增大,染料转化率和COD去除率均随之增加-当电流密度由70mA/cm2增加到90 mA/cm2时,染料转化率和COD去除率增加趋势减缓;溶液pH对染料降解有影响,弱酸性桃红BS溶液在强酸和强碱条件下的降解效果较好,pH在3.98～7.99时,染料转化率和COD去除率变化不大;染料转化率和COD去除率均随着电解时间呈递增关系,3.0 h后上升趋势逐渐减缓;支持电解质为NaCl时,能使染料转化率迅速提高,但其COD去除率不是很高;支持电解质为KNO3时,能显著提高弱酸性桃红BS溶液的COD去除率,0.5 h时COD去除率达到83%以上.另外,通过加入羟自由基清除剂叔丁醇的研究表明,在弱酸性桃红BS的降解过程中,有羟自由基产生并参与了催化降解反应.     

吸附-电催化氧化降解气态氯苯

采用高接触面积微孔曝气的方式,以吸附性多孔导电材料活性炭纤维（ACF）为电极,吸附电催化氧化两步联动降解气态氯苯,实现了在电解质水溶液中对高浓度非水溶性气态挥发性有机废气的有效处理。正交实验和单因素分析实验结合,确立最佳实验条件并着重考虑pH值、鼓气速率、电解电压、电解质浓度等因素对去除率的影响。在最佳实验条件下,气相中氯苯去除率达到74.3%（20℃）和72.9%（10℃）     

直接电解法处理染料废水的研究

实验以Ti为基体，分别采用热分解法和阳极电沉积法制备了SnO2和PbO2电极。用XRD、SEM、XPS和稳态极化、循环伏安法分别对上述电极进行结构特性表征和电化学特性检测。实验结果表明，在相同工作条件下，SnO2电极的析氧电势比PbO2电极高300～500mV，且其作为阳极降解的直接染料(直接橙S和直接耐晒黑G)模拟废水COD值下降速度快。在模拟染料废水处理体系中，提高反应温度有利于染料的降解。SnO2电极阳极氧化染料溶液过程中，能定性检测到降解产物——CO2。     

直接电解法处理染料废水的研究

实验以Ti为基体 ,分别采用热分解法和阳极电沉积法制备了SnO2 和PbO2 电极。用XRD、SEM、XPS和稳态极化、循环伏安法分别对上述电极进行结构特性表征和电化学特性检测。实验结果表明 ,在相同工作条件下 ,SnO2 电极的析氧电势比PbO2 电极高 30 0～ 5 0 0mV ,且其作为阳极降解的直接染料 (直接橙S和直接耐晒黑G)模拟废水COD值下降速度快。在模拟染料废水处理体系中 ,提高反应温度有利于染料的降解。SnO2 电极阳极氧化染料溶液过程中 ,能定性检测到降解产物———CO2 。     

光电催化去除柠檬酸铵中的氨氮

采用阳极氧化法制备了二氧化钛纳米管电极,以制备的二氧化钛纳米管电极为光阳极,采用钛片作为阴极,通过光电催化氧化方法对柠檬酸铵中氨氮进行了去除研究。考察了外加偏压、初始pH值、初始柠檬酸铵浓度,电解质的浓度对氨氮去除的影响。结果表明:与传统的光催化法和电化学法相比,光/电法在柠檬酸铵中氨氮降解过程中存在良好的协同效应;在电压为1.0 V,pH为12,Na Cl浓度为0.1 mol·L~(-1),初始投加柠檬酸铵的量以N计为25 mg·L~(-1)的条件下,紫外光照射下,采用二氧化钛纳米管电极,反应120 min后,柠檬酸铵中氨氮的降解达到60%左右。其中,柠檬酸铵中氨氮的降解产物中N2占82.6%。Ca Cl2对降解柠檬酸铵起到了加速活化作用。     

曝气量对悬浮系统单级自养脱氮性能的影响

通过连续实验和间歇实验研究了不同曝气量对SBR系统自养脱氮性能的影响。连续实验表明,在进水氨氮浓度为155～185 mg/L时,曝气量分别为20、28、36和44 L/h时,TN去除率分别为80%、82%、80%和77%;增大和减小曝气量均会降低系统的脱氮效率。间歇实验表明,随着曝气量的增加,氨氮的降解速率有所升高,20、28、36和44 L/h曝气条件下氨氮的降解速率分别为7.23、7.25、7.86和7.95 mg/(g MLVSS.h);在降解的过程中DO浓度一直维持在较低的水平(<0.5 mg/L),pH值则呈先升高后降低的趋势;氨氮降解结束时,pH值和DO浓度同时升高。结果表明,改变曝气量会影响单级自养脱氮反应的进程,但对降解过程DO浓度值变化不大;DO浓度和pH值变化对氨降解结束具有指示作用。     

电解质种类对电催化氧化降解苯酚的影响

研究了不同电解质对有机物电催化氧化性能的影响。以高温热解法制备了Ti/SnO2+Sb2O3阳极,用SEM和XRD对电极结构进行了表征。以苯酚为目标有机物,考察了Na2SO4、NaCl和NaNO33种不同电解质对苯酚降解效果的影响。用循环伏安法研究了苯酚在不同支持电解质条件下的电化学行为。采用碘量法测定了在不同电解质溶液中氧化性物质的生成量。研究结果表明,电极的活性涂层主要由SnO2和微量的Sb2O3组成,均匀完整地覆盖住了Ti基体表面。以NaCl为支持电解质时苯酚降解效果明显优于用Na2SO4、NaNO3为支持电解质,并且苯酚的降解主要以电极表面电化学生成的HClO和ClO-的间接化学氧化为主。以Na2SO4为支持电解质时有利于降低和稳定槽电压。在3种电解质条件下,苯酚的降解均遵循一级反应动力学规律。在降解过程中NaCl溶液中生成的氧化性物质浓度最大,且随降解时间延长逐渐增大。     

Ti/BDD/PbO2复合电极在化学需氧量测定中的应用

以钛基掺硼金刚石为基体,采用电沉积的方法制备了Ti/BDD/PbO2复合电极,并将其用于化学需氧量(COD)的测定。采用扫描电子显微镜(SEM)和X射线衍射谱图(XRD)表征了电极的微观形貌及结构,采用电化学工作站考察了电极对有机物响应特性。实验结果表明,在1.45 V的低电位条件下,线性范围为0.5～175 mg/L,检测限为0.3 mg/L(S/N=3)。采用Ti/BDD/PbO2复合电极测定法和重铬酸钾标准方法对市政污水、食品废水及印染废水的对比结果表明,2种方法的相对误差小于10%,具有良好的一致性。     

Ti/BDD/PbO_2复合电极在化学需氧量测定中的应用

以钛基掺硼金刚石为基体,采用电沉积的方法制备了Ti/BDD/PbO2复合电极,并将其用于化学需氧量（COD）的测定。采用扫描电子显微镜（SEM）和X射线衍射谱图（XRD）表征了电极的微观形貌及结构,采用电化学工作站考察了电极对有机物响应特性。实验结果表明,在1.45 V的低电位条件下,线性范围为0.5～175 mg/L,检测限为0.3 mg/L（S/N=3）。采用Ti/BDD/PbO2复合电极测定法和重铬酸钾标准方法对市政污水、食品废水及印染废水的对比结果表明,2种方法的相对误差小于10%,具有良好的一致性。     

PbO2电极的改性及其在难降解有机废水电化学处理中的应用

电化学方法处理难降解有机废水是一种很有前途的技术,其应用的关键是开发出高效、稳定、低成本的电极材料.PbO2电极在工业领域具有广泛的应用基础,具有较高的析氧电势和电催化活性,被认为在电化学处理难降解有机废水方面有重要的应用前景.本文对PbO2电极制备方法与改性以及在难降解有机废水电化学处理中应用的研究成果和最新进展进行了综述,并对该研究领域今后的发展趋势进行了分析.     

Influence of metal oxides on PCDD/Fs formation from pentachlorophenol

Chlorophenols (ClPhs) are considered as important precursors for PCDD/Fs formation. The influences of series of metal oxides including MgO, Al2O3, CaO, BaO, TiO2, V2O5, MnO2, Fe2O3, Co3O4, CuO, Ag2O, ZnO, HgO, SnO, PbO, La2O3, CeO2, and Eu2O3 on PCDD/Fs formation from pentachlorophenol (PCP) were investigated in a laboratory-scale reactor. The results indicated that most of the above metal oxides have obvious suppressing effects on the total amount of PCDD/Fs formation from precursor PCP except for CuO, ZnO, MnO2, TiO2 and Co3O4 with promotion effects at 280 degrees C for 2 h. Although MgO, Al2O3, Fe2O3, PbO, La2O3 and Eu2O3 could reduce the amount of octachlorinated dibenzo-p-dioxin (OCDD), they promote the formation of more toxic 1,2,3,4,6,7,8-HpCDD at the same time. The total suppressing efficiencies of several metal oxides including CaO, BaO, PbO, Ag2O, HgO and SnO which have lower Z/r (charge to radius ratio) <2 are all over 90%. The theories of generalized acid-base and atomic parameter (Z/r) were used to speculate the effecting mechanisms. The factors including time and temperature on suppressing efficiencies of CaO, BaO and PbO have also been studied in the present paper. The results showed that the total suppressing efficiencies of CaO, BaO and PbO increase with the increase of heated time and temperature.     

Transformation of hazardous lead into aluminosilicate ceramics: structure evolution and lead leaching

This study investigated crystallization mechanisms for the formation of lead aluminosilicate by sintering lead stabilization with kaolin-based precursors. PbAl2Si2O8 was found to be the only stable lead aluminosilicate in low-PbO system and demonstrates its highly intrinsic resistance to acid attack in leaching test. A three-stage PbAl2Si2O8 formation mechanism was supported by the results of the changing temperature in the system. Amorphization of sintered products was observed in both PbO/kaolinite and PbO/mullite systems at 600–700°C. When the temperature was increased to 750–900°C, the crystallochemical formation of lead aluminosilicates (i.e., Pb4Al4Si3O16, Pb6Al6Si2O21, and PbAl2Si2O8) was observed. Pb4Al4Si3O16 and Pb6Al6Si2O21 were found to be the intermediate phases at 700–900°C. Finally, PbAl2Si2O8 was found to be the only crystallite phase to host Pb at above 950°C. A maximum of 80% and 96.7% Pb can be incorporated into PbAl2Si2O8 in PbO/kaolinite and PbO/mullite systems, respectively, but the final products exhibited different microstructures. To reduce environmental hazard of lead, this strategy demonstrated a preferred mechanism of immobilizing lead into PbAl2Si2O8 structure via kaolin-based precursors.     

Heavy metal tolerance of rice plants (Oryza sativa L.) to some metal oxides at the critical levels

The toxicity of metal oxides (CdO, ZnO, PbO) were compared with each other and the critical levels of metal uptake by rice plants were determined. The order of metal toxicity to rice plants is CdO greater than ZnO greater than PbO. The highest concentration obtained for unpolished rice was 4.97 micrograms/g at the Cd 10,000 ppm in soil. This values is higher than every other we have seen in the reports for treatment with CdO. We are able to find out that the concentration of 10,000 ppm Cd in the form of CdO in the critical one towards rice plant. By contrast, such damage was not observed at even higher levels of ZnO and PbO were considered to have low toxicity toward rice plant. Also, a negative correlation between Zn or Cu accumulation in rice plants and Cd concentration in soil was found.     

Airborne foliar transfer of particular metals in Lactuca sativa L.: translocation,phytotoxicity, and bioaccessibility

The uptake, translocation, and human bioaccessibility of metals originating from atmospheric fine particulate matters (PM) after foliar exposure is not well understood. Lettuce (Lactuca sativa L.) plants were exposed to micronic PbO, CuO, and CdO particulate matters (PMs) by the foliar pathway and mature plants (6 weeks old) were analyzed in terms of: (1) metal accumulation and localization on plant leaf surface, and metal translocation factor (TF) and global enrichment factor (GEF) in the plants; (2) shoot growth, plant dry weight (DW), net photosynthesis (Pn), stomatal conductance (Gs), and fatty acid ratio; (3) metal bioaccessibility in the plants and soil; and (4) the hazard quotient (HQ) associated with consumption of contaminated plants. Substantial levels of metals were observed in the directly exposed edible leaves and newly formed leaves of lettuce, highlighting both the possible metal transfers throughout the plant and the potential for human exposure after plant ingestion. No significant changes were observed in plant biomass after exposure to PbO, CuO, and CdO-PMs. The Gs and fatty acid ratio were increased in leaves after metal exposure. A dilution effect after foliar uptake was suggested which could alleviate metal phytotoxicity to some degree. However, plant shoot growth and Pn were inhibited when the plants are exposed to PbO, and necrosis enriched with Cd was observed on the leaf surface. Gastric bioaccessibility of plant leaves is ranked: Cd?>?Cu?>?Pb. Our results highlight a serious health risk of PbO, CuO, and CdO-PMs associated with consumption of vegetables exposed to these metals, even in newly formed leaves in the case of PbO and CdO exposure. Finally, the study highlights the fate and toxicity of metal rich-PMs, especially in the highly populated urban areas which are increasingly cultivated to promote local food.

     

Palladium-facilitated electrolytic dechlorination of 2-chlorobiphenyl using a granular-graphite electrode

Palladium-assisted electrocatalytic dechlorination of 2-chlorobiphenyl (2-Cl BP) in aqueous solutions was conducted in a membrane-separated electrochemical reactor with granular-graphite packed electrodes. The dechlorination took place at a granular-graphite cathode while Pd was electro-deposited from the K2PdCl6 in the solution and at a Pd-deposited granular-graphite electrode. Using the Pd-deposited graphite cathode in the membrane reactor for a sequence of experiments, each was conducted under a lower current than in the previous one, and the rate of dechlorination became slower in each consecutive experiment. At the end of this sequence, a duplicate experiment showed a loss of activity of the Pd-deposited granular-graphite cathode. In the experiments of dechlorination while Pd was deposited at the granular-graphite electrode, the rate of dechlorination increased with increases of the initial K2PdCl6 concentration and of the applied cathode potential. In each experiment, the dechlorination of 2-Cl BP was relatively fast at the beginning, as demonstrated in an experiment in which 66.4% of 2-Cl BP was dechlorinated within 4h, but the rate of dechlorination decreased over the time. This decrease can be described with two stages of exponential decrease. The values of the rate constant in the first stage varies with the applied potential and the initial K2PdCl6 concentration, but the values of the rate constant in the second stage do not show any dependence on the potential and the K2PdCl6 concentration. The current efficiency of dechlorination was improved by applying part-time current to the electrodes.     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.