咪唑离子液体对铜在硫酸溶液中的缓蚀作用

采用动电位极化和电化学阻抗谱技术研究了三种新型烷基咪唑离子液体, 1-丁基-3-甲基咪唑硫酸氢盐([BMIM]HSO₄), 1-已基-3-甲基咪唑硫酸氢盐([HMIM]HSO₄), 1-辛基-3-甲基咪唑硫酸氢盐([OMIM]HSO₄), 对铜在0.5 mol·L_-1 H₂SO₄溶液中的缓蚀作用. 实验结果表明: 咪唑离子液体能有效抑制铜在硫酸溶液中的腐蚀, 相同浓度下的缓蚀效率大小顺序为[OMIM]HSO₄>[HMIM]HSO₄>[BMIM]HSO₄. 动电位极化表明三种咪唑化合物的加入对铜的阴阳极腐蚀过程均有抑制作用, 属于混合型缓蚀剂. 电化学阻抗谱用带两个常相位原件的等效电路对含两个时间常数的体系进行拟合, 发现咪唑化合物的添加会引起电荷传递电阻和双电层电容等阻抗参数的变化, 表明此类化合物通过吸附于铜电极与溶液界面起到缓蚀作用, 且这种吸附符合Langmuir吸附等温关系. 吸附过程热力学计算说明咪唑化合物在铜表面发生了自发的物理吸附.     

合金元素Nd对Pb-Ag阳极在H2SO4溶液中电化学行为的影响

采用循环伏安、线性扫描、电化学阻抗和环境扫描电镜对比研究了Pb-Ag和Pb-Ag-Nd阳极的阳极膜和析氧反应. 结果表明,合金元素Nd促进了Pb/PbO_n/PbSO₄ (1≤n<2)膜层的生长. 在高极化电位区间(高于1.20V (vs Hg/Hg₂SO₄/饱和K₂SO₄溶液)),Nd有利于低价铅的化合物(PbO_n,PbSO₄)向α-PbO₂和β-PbO₂转变. 此外,环境扫描电镜形貌和线性扫描分析证明Pb-Ag-Nd表面生成的阳极膜较Pb-Ag的阳极膜更厚且更致密. 因此,Pb-Ag-Nd阳极表面的阳极膜可以给合金基底提供更好的保护. 另一方面,电化学阻抗测试揭示了两种阳极的析氧反应均受中间产物的形成和吸附控制. Nd可以降低阳极膜/电解液界面处中间产物的吸附阻抗且增加中间产物的覆盖率,从而提高析氧反应活性. 综上所述,合金元素Nd可提高Pb-Ag阳极的耐腐蚀性,降低阳极电位进而起到节能降耗的作用.     

Ni/NiCo2O4电极的制备及其析氧反应性能

采用溶胶-凝胶法制备NiCo₂O₄尖晶石粉体, 然后以多孔Ni 为基体, 通过复合溶胶涂覆结合烧结制备Ni/NiCo₂O₄ 涂层电极. 运用扫描电子显微镜(SEM)、能量色散谱(EDS)和X 射线衍射(XRD)表征粉体以及Ni/NiCo₂O₄涂层电极的组成和结构. 采用循环伏安(CV), 稳态极化(LSV), 电化学阻抗谱(EIS), 恒电位阶跃以及恒电位长时间电解研究涂层电极在5 mol·L^-1 KOH溶液中的电催化析氧反应(OER). 结果表明: Ni/NiCo₂O₄涂层电极与多孔Ni 电极对比, 具有低的析氧过电位、高的比表面积和高的稳定性能; 其中比表面积增大了28.69倍,表观活化能在不同过电位分别降低了166.78和162.15 kJ·mol^-1.     

IrO2基体上阳极电沉积MnO2的电化学行为

采用极化曲线和循环伏安等电化学方法, 对不同温度下IrO₂电极在MnSO₄镀液与硫酸溶液中的电化学行为进行对比研究, 并以镀液中极化曲线上不同电流密度值进行阳极电沉积, 测量镀速大小. 研究结果表明:IrO₂电极在镀液中同时发生阳极电沉积反应和析氧副反应, 阳极电沉积反应对析氧反应具有明显的抑制作用; MnO₂的阳极电沉积过程较复杂, 存在Mn³⁺中间产物, 既有Mn³⁺→Mn⁴⁺的电沉积过程, 也有Mn³⁺的水解及水解产物的脱附的过程, 水解反应的存在严重降低了MnO₂的阳极电沉积的电流效率; MnO₂的阳极电沉积存在一定的电位区间, 在此区间, 镀速存在最大值.     

Zn(Ⅱ)在锌电极上的电沉积机理

在Zn(Ⅱ)-NH₄Cl准中性体系中,采用循环伏安法(CV)研究了Zn²⁺在锌电极上的反应方式, 通过计时电流法(CA)研究了Zn²⁺沉积的成核方式, 利用交流阻抗谱(EIS)考察了不同过电位时Zn²⁺沉积的阻抗行为。结果表明:Zn²⁺的电沉积是一个不可逆电极反应, 以两步骤单电子串联的方式进行, 第一步为速控步;电极反应的电荷传递系数与锌电极的表面结构有关。在恒电位条件下, 体系中锌电极上Zn²⁺的结晶近似于三维瞬时成核方式。Zn²⁺的沉积经历了覆盖、吸附成膜、大量晶核形成等过程, 该过程随着控制电位的负移由电化学极化过渡到电化学极化-浓差极化混合控制阶段。最后给出了Zn²⁺在锌电极上电沉积过程的机理。     

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.     

电沉积多孔复合Ni-P/LaNi5电极及其析氢电催化性能

采用复合电沉积制备了Ni-P/(LaNi₅+Al) 复合镀层, 然后将镀层浸泡在浓碱液中除铝, 成功得到多孔复合Ni-P/LaNi₅电极. 通过扫描电镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)仪等技术表征了电极的表面形貌、组成和相结构. 运用电化学线性伏安扫描(LSV)、恒电位电解、电化学阻抗谱(EIS)等手段研究了电极在20%(w) NaOH溶液中的析氢反应(HER)电催化性和稳定性. 结果表明, 与多孔Ni-P 电极相比, 多孔复合Ni-P/LaNi₅电极具有低的析氢过电位、高的比表面积和高的稳定性能; 多孔Ni-P/LaNi₅电极的析氢反应的表观活化自由能为35.44 kJ·mol^-1, 低于多孔Ni-P 的值(50.91 kJ·mol^-1).     

合金元素Nd对Pb-Ag阳极在H_2SO_4溶液中电化学行为的影响（英文）

采用循环伏安、线性扫描、电化学阻抗和环境扫描电镜对比研究了Pb-Ag和Pb-Ag-Nd阳极的阳极膜和析氧反应.结果表明,合金元素Nd促进了Pb/PbOn/PbSO4(1≤n2)膜层的生长.在高极化电位区间(高于1.20V(vs Hg/Hg2SO4/饱和K2SO4溶液)),Nd有利于低价铅的化合物(PbOn,PbSO4)向α-PbO2和β-PbO2转变.此外,环境扫描电镜形貌和线性扫描分析证明Pb-Ag-Nd表面生成的阳极膜较Pb-Ag的阳极膜更厚且更致密.因此,Pb-Ag-Nd阳极表面的阳极膜可以给合金基底提供更好的保护.另一方面,电化学阻抗测试揭示了两种阳极的析氧反应均受中间产物的形成和吸附控制.Nd可以降低阳极膜/电解液界面处中间产物的吸附阻抗且增加中间产物的覆盖率,从而提高析氧反应活性.综上所述,合金元素Nd可提高Pb-Ag阳极的耐腐蚀性,降低阳极电位进而起到节能降耗的作用.     

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.     

中温固体氧化物燃料电池阴极材料LaBiMn2O6的制备与性能研究

采用固相法合成了中温固体氧化物燃料电池(IT-SOFCs)阴极材料LaBiMn₂O₆,并利用X射线衍射(XRD)和电化学阻抗谱(EIS)进行表征.结果表明该材料与电解质Ce_0.7Bi_0.3O_1.85(CBO)在1 000 ℃烧结12 h不发生反应.交流阻抗和直流极化测试结果发现,阴极极化电阻随测试温度的增加而逐渐减小,700 ℃空气中的极化电阻为0.71 Ω·cm²;氧分压测试结果显示,在600~700 ℃范围内,电极反应的速率控制步骤为电极上发生的电荷转移反应.电极过电位为85 mV时,700 ℃的阴极电流密度达到 216 mA·cm^-2 ,表明LaBiMn₂O₆是一种潜在的中温固体氧化物燃料电池(IT-SOFCs)阴极材料.     

Influence of [BMIM]HSO4 on electrodeposition and corrosion behavior of Zn coatings from acidic sulfate bath

The effect of 1‐butyl‐3‐methylimidazolium hydrogen sulfate‐[BMIM]HSO₄ on the nucleation and growth of zinc from acidic sulfate bath was investigated at a glassy carbon (GC) electrode using cyclic voltammetry, chronoamperometric and scanning electron microscopy techniques. Dimensionless chronoamperometric current‐time transients for the electrodeposition of zinc on GC from the bath free of [BMIM]HSO₄ were in good accord with the theoretical transients for the limiting case of instantaneous three‐dimensional nucleation with diffusion‐controlled growth of the nuclei. The addition of [BMIM]HSO₄ was found to have a blocking effect on the electrodeposition of zinc and led to decrease of the nucleation and growth rate of nuclei. In addition, the instantaneous nucleation mechanism observed in the additive‐free bath was changed to a more progressive one when [BMIM]HSO₄ was present in the bath. Surface morphology analysis indicated that [BMIM]HSO₄ can induce the formation of finer grained deposits by the adsorption of additive in the first stages of deposition. The corrosion behavior of Q235 steel with coating by a thin layer of zinc in the absence and presence of [BMIM]HSO₄ was examined in 3.5% NaCl solution. The Zn coating obtained from the additive‐containing baths exhibited more excellent protection of the base metal in comparison to the additive‐free one. Copyright © 2012 John Wiley & Sons, Ltd.     

Stearate as a green corrosion inhibitor of magnesium alloy ZE41 in sulfate medium

The efficiency of stearate as a corrosion inhibitor for magnesium alloy ZE41 has been studied in sodium sulfate medium, employing electrochemical techniques like potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results of polarization study imply that stearate functions as a mixed-type corrosion inhibitor with a predominant anodic control. The adsorption of stearate on alloy surface is found to obey the Langmuir adsorption isotherm. The proposed inhibition mechanism involved adsorption of stearate onto metal surface, followed by precipitation of magnesium stearate within the microdefects of Mg(OH)₂ surface film which enhanced the barrier effect of an otherwise porous partially protective film.     

Effects of Sodium Sulfate as Electrolyte Additive on Electrochemical Performance of Lead Electrode

Sodium sulfate as an electrolyte additive was studied via electrochemical methods including linear sweep voltammetry(LSV), cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) to deeply understand its effect on the hydrogen evolution current and overpotential as well as the formation and structure of anodic passivation films on lead surface during the redox processes. The results achieved will be valuable to improve the cycle life and maintenance-free properties of lead-acid batteries.     

Influence of acidic ionic liquids as an electrolyte additive on the electrochemical and corrosion behaviors of lead-acid battery

The aim of this study is to introduce the application of some acidic ionic liquids (ILs) as an electrolyte additive in lead-acid batteries. A family of alkylammonium hydrogen sulfate ILs, which are different in the number of alkyl chain, is investigated with the aim to compare their effects on the electrochemical behavior of Pb–Sb–Sn alloy in sulfuric acid solution. The hydrogen and oxygen gas evolution potential and anodic layer characteristics were investigated employing cyclic and linear sweep voltammetric methods. The morphological changes of the PbSO₄ layer that formed on the electrode surface were confirmed using scanning electron microscopy. Also, potentiodynamic polarization curves, electrochemical impedance spectroscopy, and an equivalent circuit analysis were used to evaluate the corrosion behaviors of the Pb–Sb–Sn alloy in the presence of ILs. The obtained results indicate that hydrogen and oxygen evolution overpotential of lead–antimony–tin alloy increases in the solution containing IL and mainly depends on the number of alkyl chain in alkylammonium cation. It is clearly observed that the morphology of PbSO₄ layer changes under the influence of ILs. The corrosion studies show an increase in corrosion resistance of lead alloy in the presence of some ILs. Also, the electrochemical effects of ILs in conversion of PbSO₄ to PbO₂ and vice versa were investigated by carbon-PbO paste electrode. Cyclic voltammogram of carbon-PbO electrode shows that in the presence of ILs, oxidation and reduction peak currents increase, while reversibility decreases.     

La1－xSrxNi1－yCoyO3双功能氧电极的电化学性能

采用溶胶-凝胶法制备了一系列La1－xSrxNi1－yCoyO3（x=0、0.1、0.2、0.5； y=0～1.0）型的钙钛矿催化剂，并以活性碳为载体制备双功能氧电极.对催化剂进行了XRD结构分析以及XPS表面分析.采用三电极体系测试了氧电极的稳态极化曲线和电化学交流阻抗谱并对其阴极极化和阳极极化谱图进行了分析.实验表明，对于LaNiO3化合物，B位掺杂可显著提高催化剂表面的B离子浓度, 从而提高电催化性能；而A位掺杂由于导致有序化氧空位的增多和电导的降低而造成活性下降.电极氧还原反应的极化主要由电荷转移反应和能斯特扩散过程造成.     

曲唑酮的两步法制备及对碳钢的缓蚀机理

以3-氯苯胺、N-氯丙基二乙醇胺和吡啶三唑酮为原料，两步法制备出曲唑酮（TZD）.通过动态失重、极化曲线与电化学阻抗谱研究了TZD在0.5 mol/L盐酸溶液中对20#钢的缓蚀性能；借助扫描电子显微镜、原子力显微镜、衰减全反射红外光谱与吸附活化参数分析研究了TZD在碳钢表面的作用机理.结果表明，TZD可显著降低碳钢在盐酸溶液中的腐蚀速率，缓蚀率随TZD添加浓度的增加而增大，随温度升高而降低；298 K下，添加6 mmol/L TZD时，缓蚀率达95.8%；TZD可自发吸附组装于碳钢表面，同时抑制腐蚀反应的阴、阳极过程，显著增加界面极化阻抗；吸附为放热过程，符合Langmuir等温式.理论计算结果显示，TZD倾向以平行取向组装于碳钢表面.     

硫酸溶液中1,1’-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强效应

The inhibition effect of 1,1’-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel (MS) in 0.5 mol·L -1 H2SO4 solution was studied with the help of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization resistance (LPR) techniques. The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h. For the long-term tests, hydrogen evolution with immersion time (VH2-t) was measured in addition to the three techniques already mentioned. The thermodynamic parameters, such as adsorption equilibrium constant (Kads) and adsorption free energy (⊿Gads) values, were calculated and discussed. To clarify inhibition mechanism, the synergistic effect of iodide ion was also investigated. The potential of zero charge (PZC) of the MS was studied by electrochemical impedance spectroscopy method, and a mechanism of adsorption process was proposed. It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI. The inhibition efficiency was discussed in terms of adsorption of inhibitor molecules on the metal surface and protective filmformation.     

Co对NiOxHy薄膜电致变色性能的影响

本文利用阴极化电沉积法在抛光镍极及ＩＴＯ玻璃表面制备了含Ｃｏ量为１６．２％的ＮｉＯｘＨｙ薄膜,薄膜厚度分别为４２ｎｍ、２１ｎｍ,采用透射光谱以及线性电位扫描、交流阻抗和阳极稳态极化曲线等测试技术,考察了Ｃｏ对ＮｉＯｘＨｙ薄膜电致变色性能的影响,光谱测试范围为３００￣２５００ｎｍ。结果发现：Ｃｏ能降低薄膜着色态在可见光区及部分近红外区的透过率,通过电压调节不仅可以调光而且可望能够控温;同时Ｃｏ还能降     

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.