FR-CNTs-PbO2/SnO2-Sb/Ti电极性能及电催化降解罗丹明B

利用碳纳米管(CNTs)的优异性能和氟树脂(FR)的憎水性能,采用电化学共沉积法制备掺杂型FR-CNTs-PbO2/SnO2-Sb/Ti复合电极.运用扫描电子显微镜(SEM)和X射线衍射(XRD)仪对该电极的形貌和组成进行表征,采用接触角仪和阳极极化曲线对电极的电化学性能进行考察.结果表明,该电极比FR-PbO2/SnO2-Sb/Ti和PbO2/SnO2-Sb/Ti电极具有更强的憎水性能和更高的O2析出电位,这将有利于提高电极的电催化性能和电流利用效率.将FR-CNTs-PbO2/SnO2-Sb/Ti电极应用于罗丹明B(RhB)的降解研究,30 mA.cm-2电流密度下,处理10μmol.L-1RhB 15 min,RhB去除率高达90.21%.相同条件下,FR-PbO2/SnO2-Sb/Ti电极对RhB的去除率仅为69.08%.且FR-CNTs-PbO2/SnO2-Sb/Ti电极的反应速率常数为0.2215 min-1,是FR-PbO2/SnO2-Sb/Ti电极(k=0.1191 min-1)的近2倍.由此可见,较强的憎水性和较高的析氧电位,增强了FR-CNTs-PbO2/SnO2-Sb/Ti电极的电化学性质和电催化效果.     

钛基SnO_2、Cr_2O_3、SnO_2/Co催化电极的制备和性能比较

以涂覆热分解法制备的DSA阳极(Ti/SnO2,Ti/Cr2O3,Ti/Co/SnO2),表面晶体颗粒饱满,分布均匀致密,覆盖度好,裂缝较少,催化活化性能明显增加;电极寿命和未经过涂覆的钛基体相比也有显著提高.NH4-N和COD去除率提高了20%—40%.电极寿命与未经过涂覆的钛基体相比提高到50%—119.2%.Ti/SnO2电极的COD去除效率较高,Ti/Cr2O3电极的NH4-N去除效率较高。     

两种DSA电极的制备及其对有机废水降解的电催化性能

采用热分解法,以优化比例的SnCl4·5H2O,Sb2O3,Ce(NO3)2·6H2O,RuCl3为前躯体,制备了Ce掺杂的Ti基RuO2电极(RuO2/Ti)和Ti基PbO2电极(β-PbO2/Ti),并对两种DSA电极的电催化性能进行测试.结果表明,两种DSA电极均显示出良好的稳定性和抗腐蚀性,β-PbO2/Ti电极比RuO2/Ti电极具有更高的有机物氧化降解活性,但若以NaCl类作支持电解质时,RuO2/Ti电极也是一种可选电极.     

Fe掺杂PTFE-PbO2/TiO2-NTs/Ti电极的制备、表征及电催化性能

采用电沉积法制备了Fe掺杂PTFE-PbO2/TiO2-NTs/Ti、PbO2/TiO2-NTs/Ti、PbO2/Ti 3种电极,运用扫描电镜、X射线衍射仪观察表面形貌与形态,通过线性扫描伏安法在0.1 mol·L-1的H2SO4中测定电极的析氧极化曲线.以对硝基酚(p-NP)为目标污染物,考察了电极的电催化活性,在20 mA.cm-2电流密度下降解100 mg·L-1 p-NP,120 min时表观速率常数分别为0.0370 min-1、0.0265 min-1和0.0180 min-1,COD去除率分别为77.38%、74.07%、66.18%,研究发现在相同的条件下Fe掺杂PTFE-PbO2/TiO2-NTs/Ti性能更佳,矿化更完全.     

电催化氧化阳极制备及其降酚特性

以自制Ti基SnO2/Sb2O3/IrO2镀层形稳电极(Dimensionless Stable Anode)为阳极,采用电催化氧化法处理模拟含酚废水.通过涂层分析和电化学性能测试表征了自制电极特性,考察了电解质类型和浓度、电流密度、苯酚初始浓度及体系初始pH值等因素对苯酚氧化过程的影响,并探讨其降解动力学规律.结果表明,自制电极是以SnO2为基础的纳米级固熔体氧化物电极且具有较好的表面结构,运行稳定性较好.苯酚的降解主要依赖于以NaCl为电解质时产生的氯系活性物质的间接氧化作用.随着电解质浓度及电流密度的增加,苯酚降解速率随之增大;而苯酚的初始浓度越大,降解速率越慢.体系初始pH对过程影响不明显.苯酚的降解过程符合一级反应动力学。     

长寿命Ti/TiO_2/SbO_2-SnO_2/SnO_2-Sb-CeO_2制备及电催化废水性能

使用电镀法制备了含SbO2-SnO2中间层的TiO2/SbO2-SnO2/SnO2-Sb-CeO2电极.采用扫描电镜(SEM)、X射线衍射仪(XRD)、电化学工作站等分析仪器研究了中间层对电极表面结构、组分和电化学性能的影响.在大电流密度下测定了电极的强化使用寿命,并以酸性黑10B为模拟污染物研究了电极的电催化性能.研究结果表明,SbO2-SnO2中间层可有效改善电极表面结构,从而影响电极的寿命和催化性能.相比不含中间层的TiO2/SnO2-Sb-CeO2电极,加入SbO2-SnO2中间层后,电极表面的活性层更加致密和平整,寿命增加了10倍,对酸性黑10B的降解速率提高了一倍.     

树枝状微纳米银催化剂对甲醛的电化学检测

在Ag(NH3)2+溶液中,在钛基体上电沉积出具有新颖树枝状结构的微纳米银材料,探讨了K+或Ca2+的存在对这种树枝状微纳米银材料的影响.结果表明,在Ca2+存在下形成了尺寸更小的树枝状银(Ag/Ca2+/Ti),研究了这种钛基树枝状微纳米银电极(Ag/Ca2+/Ti)在碱性溶液中对甲醛氧化的电催化活性.循环伏安结果表明,在0.1 mol.L-1NaOH溶液中,甲醛氧化的起始电位为-0.83 V,阳极氧化电流密度随甲醛浓度的增大而明显增加;-0.5 V时的恒电位阶跃研究表明,甲醛浓度和它的稳态氧化电流密度呈现良好的线性关系,甲醛检测灵敏度为1.25 mA.cm-2(mmol.L-1)-1,检测下限18.9μmol.L-1,且乙醛、乙醇和正丁醇的干扰较小.结果表明,电沉积制备的这种细树枝状微纳米银电极(Ag/Ca2+/Ti)对甲醛氧化具有强的电催化活性,且对甲醛检测具有高灵敏度和较好的选择性,有望作为甲醛检测的电化学传感器.     

新型双槽光电化学反应器对活性艳红的降解研究

用热氧化法制备了TiO2/Ti薄膜电极,并用XRD和AFM对TiO2/Ti薄膜电极的晶形和表面形貌进行了表征。结果表明：热氧化法制备的TiO2主要为锐钛型纳米颗粒,直径在40 nm左右。设计了一种新型双槽光电化学反应器,用于废水的处理。以热氧化法制备的TiO2/Ti薄膜电极为阳极进行光电催化反应,同时以石墨电极为阴极用于产生双氧水,并与紫外光组成UV/H2O2体系。考察了双槽反应器中活性艳红X-3B在不同条件下的降解效果。降解结果表明：在新型反应器的阴阳两极槽中,活性艳红不仅在TiO2/Ti阳极槽中被降解,而且在石墨阴极槽中也得到降解;活性艳红在酸性条件下的降解效果最好;相对于单纯的电化学氧化和光催化,光电化学协同作用对X-3B的降解效果最好。     

微生物燃料电池还原二氧化铅及产电研究

为探究二氧化铅在微生物燃料电池(Microbial fuel cell,简称MFC)中的还原及对产电性能的影响,采用电沉积法成功制备了钛基二氧化铅(PbO2/Ti),并将其作为阴极材料应用于双室MFC.二氧化铅的价态、晶型、形态特征以及电化学特性分别采用X射线光电子能谱(XPS)、X射线衍射光谱(XRD)、扫描电子显微镜(SEM)和循环伏安扫描(CV)进行分析,MFC的产电能力通过COD的去除、输出电压和极化曲线进行表征.结果显示,在以PbO2/Ti为阴极的MFC中COD的降解率可以达到87.68%,明显高于纯钛板的对照(71.4%).当外阻为1 000Ω时,最大输出电压达到760 mV,约为对照的30倍.最大功率密度达379 mW m–2,相应的电流密度为1 185 mA m–2.同时,PbO2被还原为PbO和Pb3(PO4)2.由此可见,二氧化铅由于其具有的强氧化性可作为廉价高效的阴极材料应用于MFC,从而大大提高MFC产电能力.     

Ti/Sb-SnO2功能电极的制备及电化学处理废水的性能

采用热分解法制备了Ti/Sb-SnO2电极,并用XRD、SEM对电极涂层进行表征.研究了涂层次数对于析氧过电位的影响,应用阳极快速寿命测试法测试了Ti/Sb-SnO2电极的使用寿命,通过极化曲线考察了电极的析氧过电位.采用该电极对甲基橙模拟废水进行了电化学降解实验,并考察此电极处理实际废水的效果.研究表明,随着涂层次数...     

Cr/γ-Al_2O_3对乙酸乙酯的催化燃烧

使用浸渍法制备不同负载量的Cr/γ-Al_2O_3催化剂,研究乙酸乙酯的催化燃烧.BET,XRD结果表明,Cr在γ-Al_2O_3上负载存在分散阈值效应,负载量在阈值以下时呈单层分散形式,在超过阈值时Cr形成结晶,实验测得单层分散阈值与理论计算一致.Raman结果表明Cr在单层分散时为Cr~(6+),而在非单层分散时为Cr_2O_3.催化乙酸乙酯燃烧的活性研究显示,阈值效应对催化活性有显著影响:催化活性在单层分散阈值时最好,此时活化能最高,指前因子最大.     

Clean electrochemical deposition of calcium carbonate to prevent scale formation in cooling water systems

Calcium carbonate (CaCO₃) deposited in water systems leads to scale formation, decreases flow rate, reduces heat transfer and favors microbial proliferation of toxic bacteria such as Legionella. This issue may be solved by electrochemical deposition, without adding toxic chemicals. Therefore, we studied here the deposition of CaCO₃ by electrochemical reduction of oxygen into hydroxide ions with stainless steel and titanium (Ti) working electrodes. Analysis was done using cyclic voltammetry, chronoamperometry, dynamic impedance spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (EDX) coupled with X-ray diffraction (XRD). Results show that optimal formation of CaCO₃ is done at ?1.2 V with the stainless steel electrode and at ?1.4 V for the Ti electrode. More negative potentials induce the formation of calcite. Using the Ti electrode, we found that aragonite is the major form (82 %), with only one capacitive loop. Using the stainless steel electrode at 1.2 V, we found 47 % of aragonite and 38 % of calcite. Overall, our findings demonstrate the feasibility of the electrochemical deposition of CaCO₃ in cooling water systems, without the addition of any chemical.     

腐植酸臭氧氧化和过氧化氢催化氧化处理特性比较

以TOC和UV254为指标,比较了不同条件下腐植酸的臭氧氧化和过氧化氢催化氧化效果,运用HPLC和热裂解-GC-MS分析考察了氧化前后有机物分子量分布和官能团构造的变化情况．研究结果表明：过氧化氢和臭氧单独作为氧化剂对水中TOC基本上没有去除作用,但均能导致水中UV254浓度的降低;在几种催化剂的作用下,过氧化氢对TOC和UV254的去除效果明显提高,其中以O3作为催化剂的效果最好,Fe^2＋次之,而Mn^2＋和Cu^2＋的催化效果较差;过氧化氢催化氧化和臭氧化均导致有机物分子量分布向小分子的方向转移,氧化后水中以羧酸、醇、胺、酯、醚、烷烃为代表的含氧基团和饱和构造基团明显增多;过氧化氢催化氧化和臭氧氧化均有助于改善混凝处理和活性炭吸附处理的效果．关键词腐植酸,臭氧,过氧化氢,催化氧化．     

Electrocatalytic debromination of BDE-47 at palladized graphene electrode

Graphene electrodes （Ti/Gr） were prepared by depositing Gr sheets on Ti substrate, followed by an annealing process for enhancing the adhesion strength. Electrochemical impedance spectroscopies and X-ray dif- fraction patterns displayed that the electrochemical behavior of Ti/Gr electrodes can be improved due to the generation of TiO2 layer at Ti-Gr interface during the annealing process. The palladized Gr electrodes （Ti/Gr/Pd） were prepared by electrochemical depositing Pd nanoparticles on Gr sheets. The debromination ability of Ti/Gr/Pd electrodes was investigated using BDE-47 as a target pollutant with various bias potentials. The results indicated that the BDE-47 degradation rates on Ti/Gr/Pd electrodes increased with the negative bias potentials from 0V to -0.5 V （vs. SCE）. Almost all of the BDE-47 was removed in the debromination reaction on the Ti/Gr/Pd electrode at - 0.5 V for 3 h, and the main product was diphenyl ethers, meaning it is promising to debrominate completely using the Ti/Gr/Pd electrode. Although the debromination rate was slightly slower at -0.3 V than that under -0.5 V, the current efficiency at -0.3 V was higher, because the electrical current acted mostly on BDE-47 rather than on water.     

Efficient dechlorination of 2,4-dichlorophenol in an aqueous media with a mild pH using a Pd/TiO2NTs/Ti cathode

In this study, palladium-loaded titania nanotubes was fabricated on a titanium plate (Pd/TiO₂NTs/Ti) for efficient electrodechlorination of 2,4-chlorophenol with a mild pH condition. The nature of Pd/TiO₂NTs/Ti electrodes was characterized by field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) techniques. The characterization results indicated the generation of Pd⁰ nanoparticles which were evenly dispersed on titania nanotubes arrays on the Pd/TiO₂NTs/Ti surface. An effective degradation efficiency of up to 91% was achieved within 60 min at cathode potential of −0.7 V (vs. SCE) and initial pH of 5.5. The effects of the applied cathode potential and initial pH on the degradation efficiency were studied. A near neutral condition was more favorable since very low and very high pHs were not conducive to the dechlorination process. Furthermore, the intermediates analysis showed that the Pd/TiO₂NTs/Ti electrode could completely remove chlorine from 2, 4-dichlorophenol since only phenol was detected as the byproduct and the concentration of released chlorine ions indicated near-complete dechlorination. This work presents a good alternative technique for eliminating persistent chlorophenols in polluted wastewater without maintaining strong acidic environment.     

Temperature and metabolic rate in sedentary fish from the Antarctic,North Sea and Indo-West Pacific Ocean

Resting metabolic rate was measured in demersal stages of the teleostNotothenia neglecta Nybelin from the South Orkney Islands, Antarctica, from 1985 to 1987. The relationship between and body mass (Mb) conformed to the general relationship , wherea is a proportionality constant andb is the scaling exponent. (mg O₂ h^–1) was found to scale toMb ^{(0.82±0.011)} in the summer (November to April, 1.6 to 1 850 g,n=56) and toMb ^{(0.76±0.013)} in the winter (May to October, 0.9 to 1 850 g,n=57) (values ofb are means ± SD). Although the scaling exponents were significantly different (P<0.01), was similar in the juvenile stages of summer- and winter-caught fish matched for body mass. The effects of activity on oxygen consumption was studied using a Brett respirometer. Adult stages had a factorial aerobic scope for activity of 5.7, which is similar to that reported for demersal fish from temperate latitudes. The effects of temperature on resting metabolism was investigated in fish with similar sedentary lifestyles from the North Sea (Agonus cataphractus andMyoxocephalus scorpius) and the Indo-West Pacific (Paracirrhites forsteri, P. arcatus, Neocirrhites armatus andExallias brevis). Extrapolated values of for the tropical species approached zero at 5 to 10°C. For a standard 50 g fish, for the tropical species at 25°C was in the range 3.4 to 4.4 mg O₂ h^–1, compared with 1.3 mg O₂ h^–1 forNotothenia neglecta at its acclimation temperature. Thus, the maximum metabolic rate of sedentary tropical species at 24°C is likely to be 2 to 4 times higher than inN. neglecta at 0°C. This suggests that the energy available for sustained activity is significantly lower in cold- than in warm-water fish.     

Mechanisms behind the accelerated extracellular electron transfer in <Emphasis Type="Italic">Geobacter sulfurreducens</Emphasis> DL-1 by modifying gold electrode with self-assembled monolayers

Modification of electrode surface with carboxylic acid terminated alkanethiol self-assembled monolayers (SAMs) has been found to be an effective approach to improve the extracellular electron transfer (EET) of electrochemically active bacteria (EAB) on electrode surface, but the underlying mechanism behind such enhanced EET remains unclear. In this work, the gold electrodes modified by mercapto-acetic acid and mercaptoethylamine (Au-COOH, Au-NH₂) were used as anodes in microbial electrolysis cells (MECs) inoculated with Geobacter sulfurreducens DL-1, and their electrochemical performance and the bacteria-electrode interactions were investigated. Results showed that the Fe(CN) ₆ ^3–/4– redox reaction occurred on the Au-NH₂ with a higher rate and a lower resistance than that on the Au or the Au-COOH. Both the MECs with the Au-COOH and Au-NH₂ anodes exhibited a higher current density than that with a bare Au anode. The biofilm formed on the Au-COOH was denser than that on bare Au, while the biofilm on the Au-NH₂ had a greater thickness, suggesting a critical role of direct EET in this system. This work suggests that functional groups such as–COOH and-NH₂ could promote electrode performance by accelerating the direct EET of EAB on electrode surface.     

掺铅TiO2薄膜的光催化活性及电化学性能

采用溶胶凝胶烧结工艺在玻璃表面制备铅离子多层掺杂的光催化复合TiO2薄膜,用XRD技术表征了该薄膜的晶型,并用电化学方法测定了该薄膜电极的伏安特性及交流阻抗性能．以光催化降解甲基橙溶液为模型反应,采用两种不同方式制备的铅离子多层掺杂TiO2薄膜具有很好的光催化活性,最佳掺杂浓度均为0．5％(Pb／Ti原子百分比),PbD0.5掺铅薄膜的最佳光催化降解甲基橙表观速率常数约是纯TiO2的2．52倍．铅离子掺杂TiO2薄膜表现出近表面处捕获光生电子或空穴,随后被捕获的电子或空穴迁移到TiO2薄膜表向参与光催化反应。