镁合金在含F－的NaOH溶液中钝化行为的电化学研究

采用极化曲线、电容-电位曲线、Mott-Schottky分析以及电化学阻抗(EIS)等电化学方法研究了镁合金在含F^－ NaOH溶液中的阳极钝化行为. 结果表明, 在－1.2～1.8 V的电位范围内, 镁合金在含F^－的NaOH溶液中发生阳极钝化. 所形成的钝化膜表现出n型半导体的导电特性. 在0.7～1.8 V的电位范围内, 随着F^－浓度增大, 镁合金的阳极极化电流密度呈现出随着电位升高而逐渐增大的趋势, 随着F^－浓度增大这一趋势逐渐减弱. 并且F^－浓度的增大使得镁合金表面空间电荷层电容和钝化膜的载流子密度都不断减小. 通过极化曲线和电化学阻抗共同说明, 在5%的Na₂SO₄溶液中, NaOH溶液中阳极钝化后的镁合金随着钝化体系中F^－浓度的增加其耐蚀性逐渐减弱.     

温度对贮氢合金MlNi3.75Co0.65Mn0.4Al0.2动力学性能的影响

在-20℃～85℃的范围内系统地研究了温度对贮氢合金MINi3.75Co0.65Mn0.4Al0.2动力学性能的影响.结果表明:该贮氢合金电极的电化学反应电阻Rt,欧姆内阻Ro,阴极极化过电位,阳极极化过电位,阳极极化过程中的电化学反应过电位ηa和浓差极化过电位ηa均随温度的升高而减小,该电极的交换电流密度i0,对称因子β和电极中氢的扩散系数D随温度的升高而增大.当放电电流密度较低时,电化学反应是整个电极过程的速度控制步骤;当放电电流密度较高时,氢的扩散是整个电极过程的速度控制步骤;在中等放电电流密度下,电极过程由电化学过程和氢的扩散过程混合控制.该电极中电化学反应过程和氢扩散过程的活化能分别为28.1 kJ·mol-1和19.9 kJ·mol-1.     

乙烷质子传导膜燃料电池的极化与反应机理

制备了以乙烷作为燃料电池膜电极组装(MEA)及构建了单电池系统。研究了Nafion材料作为质子传导膜、Pt/C作为电极催化剂构成的燃料电池在105 ℃和0.4 MPa电化学性能。采用交流阻抗分析法、色谱分析法及根据Faraday定律,考察了电池的电极极化过程,确定了电池的反应产物并探讨了电极的电化学反应机理。研究结果表明,乙烷燃料电池内阻引起的欧姆极化很小,电池阴极的极化主要是欧姆极化过程所控制,阳极极化主要为活化和浓差过程控制,阳极极化比阴极极化显著,乙烷燃料电池的极化主要在阳极侧;在实验操作条件下,阴极反应产物为水,阳极反应的主产物为CO₂且含有少量的CO,电池反应产物不含乙烯。     

温度对贮氢合金MINi~3~.~7~5Co~0~.~6~5Mn~0~.~4Al~0~.~2动力学性能的影响

在-20℃～85℃的范围内系统地研究了温度对贮氢合金MINi~3~.~7~5Co~0~.~6~5Mn~0~.~4Al~0~.~2动力学性能的影响。结果表明：该贮氢合金电极的电化学反应电阻R~t,欧姆内阻R~0,阴极极化过电位,阳极极化过电位,阳极极化过程中的电化学反应过电位η~a和浓差极化过电位η~c均随温度的升高而减小,该电极的交换电流密度i~0,对称因子β和电极中氢的扩散系数D随温度的升高而增大。当放电电流密度较低时,电化学反应是整个电极过程的速度控制步骤;当放电电流密度较高时,氢的扩散是整个电极过程的速度控制步骤;在中等放电电流密度下,电极过程由电化学过程和氢的扩散过程混合控制。该电极中电化学反应过程和氢扩散过程的活化能分别为28.1kJ.mol^-^1和19.9kJ.mol^-^1。     

硫酸根离子对铁在弱碱性溶液中阳极溶解和钝化行为的影响

采用浸泡实验, 电化学测试和表面分析技术研究了硫酸根离子浓度对铁在稀碳酸氢钠溶液中开路状态和阳极极化行为的影响. 在无硫酸根离子及含有少量硫酸根离子的碳酸氢钠溶液中, 铁的开路电位约为(-0.225±0.005) V, 并呈现钝化状态, 其电化学阻抗很大, 腐蚀速率较低. 在含有较高浓度硫酸根离子的碳酸氢钠溶液中, 铁的开路电位为(-0.790±0.010) V并呈现活性溶解状态, 其电化学阻抗较小, 腐蚀速率较高, 同时阳极极化曲线上能观察到活化-钝化转变现象. 由于铁在含有较高浓度硫酸根离子的碳酸氢钠溶液中处于活化状态, 阳极极化曲线上存在数个电流峰. 足够高的硫酸根离子浓度会导致铁表面预先形成或转变而成的氧化膜失效. 相比于自然曝氧状态, 在除氧条件下较低的硫酸根离子浓度即可引起铁在碳酸氢钠溶液中由钝态向活性溶解态的转变.     

碳钢在碳酸铵溶液中的腐蚀研究实验改进

采用线性扫描伏安法和交流阻抗法研究了碳钢在不同实验条件下的腐蚀规律,碳钢在碳酸铵溶液中的阳极过程为溶解、钝化、过钝化溶解,溶解初期在电极界面的传质为线性扩散控制;随着溶液温度的升高,阻抗谱表示为单一时间常数的容抗弧,容抗弧直径逐渐减小,电阻变小,碳钢的腐蚀速度增大;Cl~-浓度越大,钝化区域变小,碳钢更容易腐蚀;加入硫脲缓蚀剂,碳钢容抗弧直径增大,电阻变大,有利于保护碳钢。     

钙钛矿型氧化物电极极化过程中的导电特性

研究了La_(0.5)Sr_(0.5)CoO_3等钙钛矿型氧化物电极的极化性质及它们对氧电化学还原的催化活性。发现在阴极极化过程中氧化物电极发生还原时,其电催化活性降低,电极阻抗明显增加,而在阳极极化过程中电极阻抗减小。讨论了影响钙钛矿型氧化物导电的因素及电极阻抗变化对电极性能的影响。     

碳钢缝隙内溶液化学和阳极极化行为研究

为研究缝隙腐蚀的溶液化学和缝中金属阳极极化行为,设计一种楔形缝隙模拟装置。以碳钢为研究对象,分别测试了在３．５％（ｗｔ）ＮａＣｌ溶液中缝内各位置的电极电位,Ｃｌ＾－浓度,ｐＨ值以及缝外阳极极化时电流密度的变化。     

碳钢在N-甲基二乙醇胺介质中的电化学阻抗谱研究

应用电化学阻抗谱(EIS)研究碳钢在N-甲基二乙醇胺(MDEA)介质中的腐蚀行为.实验表明,未经预阴极活化处理的碳钢表面存在氧化膜,溶解氧促使它腐蚀速率增大,经活化处理去除氧化膜后则相反.在不含热稳定性盐(HSS)的MDEA溶液中,碳钢的腐蚀性随MDEA浓度的增加呈先上升后下降趋势;而在HSS高含量的溶液中,其腐蚀性则随MDEA浓度的增加而单调下降.在含有HSS模拟溶液中,碳钢的阳极极化EIS随极化电位由低到高分别出现感抗、负阻抗以及Warburg阻抗响应等特征,对应于孔蚀、活化状态向钝化状态过渡以及进入钝化的趋势,腐蚀反应的阴极过程表现为电化学反应和扩散传质混合控制,阳极过程为电化学反应控制.     

酸性AlCl3-BMIC离子液体中的铝阳极溶解

采用线性扫描伏安法研究了Lewis 酸性AlCl₃-BMIC (BMIC: 1-butyl-3-methylimidazolium chloride)离子液体中铝电极的溶解. 铝电极在阳极极化时出现了钝化现象, 钝化是由于在铝电极表面形成了固体AlCl₃钝化膜造成的. 铝的电化学溶解过程可以依次分为三个区: 电化学控制区、过渡区和钝化区. 在电化学控制区, 铝的电化学溶解速率随着电位的正移而逐渐增加; 在过渡区, 由于电极表面AlCl₄^-和Al₂Cl₇^-浓度发生改变而析出固体AlCl₃使得铝电化学溶解速率随着电位的正移而逐渐减小; 当钝化膜形成之后, 铝的电化学溶解速率不再随着电位的正移而发生改变, 铝溶解进入钝化区. 增加搅拌、升高温度、降低离子液体AlCl₃摩尔分数都可以增加铝溶解阳极极限电流密度.     

Studies on the influence of various experimental conditions on electrochemical generation of ferrate(VI) in NaOH-KOH mixed electrolyte

Ferrate(VI) was prepared by electrooxidation in diaphragm electrolyzer with iron wire gauze as anode and NaOH-KOH mixed solution as electrolyte. The influences of various experimental conditions, such as the volume ratio of NaOH-KOH mixed electrolyte, temperature, current density, passivation of iron anode were investigated on ferrate current efficiency. Due to the low solubility of K₂FeO₄ in concentrated alkaline solution and the passivation of iron wire gauze anode, a highest current efficiency over 90% was obtained at 45°C and at a current density of 5 mA cm⁻² in mixed electrolyte with the volume ratio of NaOH: KOH equal to 6: 4. The result is superior to using NaOH and KOH as electrolyte respectively. In addition, polarization curves, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) were employed to further study the effects of synthesis conditions on ferrate(VI) in theory. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 853–857. The article is published in the original.     

Electrocatalytic oxidation of methanol on Pt/NiZn electrode in alkaline medium

In this study, a platinum electrode was coated with NiZn layer (Pt/NiZn) in a nickel-zinc bath by electrodeposition for use as anode material for methanol electrooxidation in alkaline solution. The electrode prepared was etched in a concentrated alkaline solution (30% NaOH) to produce a porous and electrocatalytic surface suitable for use in the methanol electrooxidation (Pt/NiZn). The surface morphologies and compositions of coating before and after alkaline leaching were determined by energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. The effect of NiZn coated platinum electrode for methanol electrooxidation was investigated in 1 M NaOH solution by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Methanol electrooxidation on Pt/NiZn electrode was studied at various temperatures and potential scan rates. The results showed that Pt/NiZn electrode behaved as an efficient catalyst for the electrooxidation of methanol in alkaline medium.     

涂液浓度对Ru-Ti-Ir氧化物阳极涂层性能的影响

应用热分解法制备了由不同浓度涂液形成的Ru-Ti-Ir氧化物阳极涂层,SEM,EDX,XRD、强化电解寿命、极化曲线、循环伏安和电化学阻抗等测试表明,涂液浓度对阳极涂层的表面形貌有着很大的影响,但不甚影响其析氯极化过程.随着涂液浓度的增加,阳极涂层的伏安电量和双电层电容都出现先降低后增加的变化趋势.     

球形微粒Co3O4电极催化氧化硫离子

尝试用氨蒸发诱导合成方法在石墨小片上生长球形Co₃O₄微粒, 并用其制备电极且进行S^2-的电化学氧化研究. 用极化曲线、恒电位技术等电化学方法考察了Co₃O₄电极对S^2-的电化学氧化的催化性能, 发现Co₃O₄电极对电化学氧化S^2-具有优异的催化性能, 极大地促进了-0.40 V 附近S^2-向含硫的酸根离子和低级多硫离子的转变, 电流密度最大可以达到580 mA·cm^-2. 恒电位极化表明电极的电催化稳定性良好; 电化学阻抗谱(EIS)测试显示Co₃O₄在碱性S^2-电解液中的电荷转移电阻很小, 这从电化学动力学角度解释了它对S^2-具有良好的催化性能.     

Anodic passivation of tin in sodium hydroxide solutions

The passivating processes at a tin anode in NaOH solutions have been investigated by voltammetry. The effects of varying sweep rate, rotation speed, concentration of NaOH and the potential limits have been studied. The results indicate that primary passivation is the results of a dissolution—precipitation mechanism involving the blocking of the electrode by Sn(II) species. There is evidence that during secondary passivation there is not only oxidation of Sn(II) to Sn(IV) species but alos the direct oxidation of Sn to Sn(IV) solution soluble species. At more positive potentials dehydration of the film may occur and result in a more efficient passivation. A possible explanation is advanced for observed current oscillations.     

Dispositif de commande des systèmes électrochimiques à états stationnaires multiples

It has been shown that electrochemical processes having more than one steady state can be studied by a generator with negative impedance. In this paper we describe a new regulating device composed from a potentiostat and a simple additive circuit; a voltage proportional to current is introduced in the reference branch of the potentiostatic circuit. Experimental data are presented for an equivalent cell (tunnel diode+resistor) and for a zinc electrode polarized in alkaline medium. The Z-shaped curve thus obtained exhibits a quasi-reversible transition between active and passive state. So, the mechanism proposed by Gabrielli et al. for anodic polarization of iron in acid medium will probably hold for zinc “passivation”.     

SrRuO3阳极催化剂的制备及对乙醇电催化氧化性能研究

用溶胶凝胶法制备了钙钛矿型氧化物SrRuO₃，热重分析和X射线衍射分别对制备过程和产物进行了分析和表征。采用循环伏安、计时电流和交流阻抗方法测试了所得产物对常温下碱性介质中乙醇电化学氧化的催化性能。循环伏安曲线、计时电流和交流阻抗结果表明：在乙醇溶液中，阳极电流密度明显大于氢氧化钾溶液中的阳极电流密度，并且随着电极中SrRuO₃含量的增加，电流密度也大幅度增加，在乙醇溶液中，SrRuO₃电极的电荷迁移阻抗明显降低。SrRuO₃对乙醇电化学氧化具有良好的催化作用。     

The use of electrochemical impedance spectroscopy (EIS) in the evaluation of the electrochemical properties of a microbial fuel cell

Electrochemical impedance spectroscopy (EIS) has been used to determine several electrochemical properties of the anode and cathode of a mediator-less microbial fuel cell (MFC) under different operational conditions. These operational conditions included a system with and without the bacterial catalyst and EIS measurements at the open-circuit potential of the anode and the cathode or at an applied cell voltage. In all cases the impedance spectra followed a simple one-time-constant model (OTCM) in which the solution resistance is in series with a parallel combination of the polarization resistance and the electrode capacitance. Analysis of the impedance spectra showed that addition of Shewanella oneidensis MR-1 to a solution of buffer and lactate greatly increased the rate of the lactate oxidation at the anode under open-circuit conditions. The large decrease of open-circuit potential of the anode increased the cell voltage of the MFC and its power output. Measurements of impedance spectra for the MFC at different cell voltages resulted in determining the internal resistance (R(int)) of the MFC and it was found that R(int) is a function of cell voltage. Additionally, R(int) was equal to R(ext) at the cell voltage corresponding to maximum power, where R(ext) is the external resistance that must be applied across the circuit to obtain the maximum power output.     

硫酸溶液中聚天冬氨酸对碳钢的吸附缓蚀性能

应用电化学极化曲线和交流阻抗研究聚天冬氨酸(PASP)对碳钢的缓蚀性能,讨论了PASP浓度和温度对缓蚀效果的影响.结果表明:PASP是一种以抑制阳极为主的缓蚀剂.在实验温度范围内,PASP在0.5mol/L硫酸溶液中对碳钢的缓蚀效率随着温度升高而降低,并以10℃时的缓蚀效果最好.在给定温度下,缓蚀率均随PASP浓度的增加而迅速增加,但当PASP质量浓度达到2.5g/L时,缓蚀率的增加趋于平缓,10℃下,缓蚀率的最高值可达80.33%(PASP 6.0g/L),PASP在碳钢表面的吸附基本服从Freund lich吸附等温式,PASP的加入增大了碳钢的腐蚀反应表观活化能.     

电镀锌钛/锆基无铬化学转化膜的制备与耐蚀性能

借助优化钛/锆基化学转化工艺,在碱性无氰镀锌层基体上获得了环保型的无铬转化膜,并与铬酸盐彩色钝化膜作对比.中性盐雾试验、动电位极化和电化学阻抗谱测试结果表明:钛/锆基化学转化膜出现白锈时间为96 h,达到铬酸盐彩色钝化膜标准,且呈现出较低的腐蚀电流和较高的极化电阻,但钝化特性不如铬酸盐彩色钝化膜明显.