KSCN对钒电池正极反应动力学及电池性能的影响

应用循环伏安、交流阻抗(EIS)等方法,研究了硫氰酸钾(KSCN)添加剂对石墨电极上(正极)钒电池电对(VO2+/VO2+)动力学特征及电池性能的影响.结果表明:1)KSCN的添加提高了VO2+/VO2+电对氧化峰的峰电流,但对还原峰的影响很小;2)添加KSCN,增加了充放电电量,提高了钒电池中活性物质的利用效率;3)VO2+/VO2+电对的速率常数K0,随着KSCN浓度的增加而逐渐增大.     

碳纸负载电极在乳液法合成聚苯胺电化学性能分析中的应用

首次采用碳纸负载聚苯胺(PAn)为工作电极,探讨了反应时间对乳液法合成PAn电化学性能(循环伏安、交流阻抗及塔菲尔曲线)的影响,并通过对产物电导率、产率及特性粘度的对比分析,印证了产物电化学性能的表征结果.实验结果表明,循环伏安曲线均能有效表征出PAn的三对氧化还原特征峰,交流阻抗曲线均出现一个几乎完整的半圆;且产物的循环伏安、交流阻抗、塔菲尔、产率及电导率随反应时间的变化趋势一致,在反应5h时,PAn的各项性能指标较好.结果显示,利用碳纸作为负载电极,可以对乳液法合成PAn的电化学性能实施有效的实时表征.     

2，2′-联吡啶In（Ⅲ）配合物与DNA作用的电化学研究

应用循环伏安法、微分脉冲伏安法和交流阻抗法研究了配合物In(bpy)Cl3·H2O与DNA在Tris-HCl缓冲溶液(pH=7.2)中的相互作用.结果表明配合物中心In(Ⅲ)离子的循环伏安曲线上呈现一对准可逆的氧化还原波,DNA与配合物作用后,配位中心离子的氧化还原峰电流明显降低,扩散系数减小,电化学反应阻抗增大,式量电位负移,表明该配合物与DNA的作用方式为静电结合.     

V(Ⅳ)/V(Ⅴ)电对在石墨毡与导电塑料复合电极上的反应机理

应用循环伏安、极化曲线和交流阻抗等电化学方法研究了V(Ⅳ)/V(Ⅴ)电对在石墨毡复合电极上反应的速控步骤.结果表明,V(Ⅳ)/V(Ⅴ)电对在石墨毡电极上的反应属准可逆过程,且氧化过程包含有后置化学转化步骤;该过程Tafel斜率的实验值为0.124,而理论计算的,以电化学步骤作为控制步骤的Tafel斜率约0.12,两者吻合很好,表明该氧化过程受电化学步骤控制;以等效电路拟合不同极化电位下的交流阻抗,得出该电化学反应阻抗远大于其他阻抗,意味着电化学过程可能是电极反应的控制步骤,与实验得到的极化曲线分析结果相一致.     

钙调素与重金属Pb2+结合反应的方波极谱与循环伏安法研究

采用方波极谱法研究了重金属Pb2+与钙调素(CaM)的结合反应, 直接检测到Pb2+-CaM配合物的存在, 并进一步利用循环伏安法研究了Pb2+-CaM的电极反应. 在pH=6.5时, 用方波极谱法在Pb2+-CaM体系中检测出2个还原峰, 峰电位分别为-0.44~-0.47 V和-0.73~-0.77 V, 说明在Pb2+-CaM体系中铅有2种存在形式, -0.44~-0.47 V的还原峰对应于游离态Pb2+, 电位更负的还原峰对应于配合物[Pb2+-CaM]. 2个还原峰的峰电流均随着cPb2+/cCaM比值增大而增大; 至cPb2+/cCaM≥10后, 配合物[Pb2+-CaM]的峰电流基本不再变化, 而游离态Pb2+的峰电流则继续增大. 利用极谱滴定曲线的拐点可判断出Pb2+在CaM中有10个结合位点. 进一步的测量结果表明, 循环伏安曲线出现游离态Pb2+的氧化峰和还原峰, 而络合态的[Pb2+-CaM]只有其还原峰, 反向电压扫描时不出现阳极波, 即没有相对应的氧化峰出现.     

Ce4+/Ce3+-V2+/V3+氧化还原流动电池的可行性研究(Ⅱ)--旋转圆盘(RDE)与旋转环盘(RRDE)法对Ce4+/Ce3+氧化还原体系的研究

用RDE与REDE法研究了Ce4+/Ce3+-V2+/V3+氧化还原流动电池中Ce4+/Ce3+体系的电化学动力学参数,以说明组成该新型氧化还原流动电池的可能性.用RDE法得出在铂电极表面与玻碳电极上均会生成一层氧化膜,对Ce3+的氧化反应产生阻碍作用.但在铂上的氧化膜对Ce4+的还原反应却有催化作用.用Rrde法得出Ce3+在玻碳电极上的氧化与析氧之间存在着竞争,为得到较高的Ce3+氧化效率,应控制氧化电流在2～8 mA@cm-2之间.     

Keggin型缺位硅钨杂多阴离子的电化学性质及电催化还原H2O2

应用循环伏安、方波伏安和交流阻抗法研究了Keggin型缺位硅钨杂多阴离子SiW11O398-(SiW11)在0.1mol.L-1NaHSO4+Na2SO4溶液中的电化学性质及其对H2O2还原的间接电催化作用.结果表明,SiW11的酸性水溶液在玻碳(GC)电极上显示两对可逆的还原-氧化波,对应的电荷迁移数均为1,且有2个质子参与反应.根据第1对波的还原峰电流与扫描速率平方根关系得到SiW11在溶液中的扩散系数DO为8.92×10-6cm2.s-1.SiW11对H2O2的还原具有明显的电催化活性,催化峰电位随溶液pH的降低而正移,峰电流增大.质子H+在催化反应中起协同促进作用.实验测定该电催化过程的均相准一级反应速率常数为0.30 s-1.SiW11电催化还原H2O2的机理被认为是经过形成所谓"七配位过氧化物"而发生的.     

2,2'-联吡啶In(Ⅲ)配合物与DNA作用的电化学研究

应用循环伏安法、微分脉冲伏安法和交流阻抗法研究了配合物In(bpy)Cl3.H2O与DNA在Tris-HCl缓冲溶液(pH=7.2)中的相互作用.结果表明:配合物中心In(Ⅲ)离子的循环伏安曲线上呈现一对准可逆的氧化还原波,DNA与配合物作用后,配位中心离子的氧化还原峰电流明显降低,扩散系数减小,电化学反应阻抗增大,式量电位负移,表明该配合物与DNA的作用方式为静电结合.     

血红蛋白模拟过氧化物酶催化H2O2氧化邻氨基酚的固体电极伏安法研究

探讨了用血红蛋白作为辣根过氧化物酶的替代物,用于催化H2O2氧化邻氨基酚的反应体系.其催化反应生成一种具有电化学活性的产物,该产物在玻碳电极上于-0.370 V(vs.Ag/AgCl)产生一个峰形良好的还原峰.还原峰电流随着血红蛋白浓度的增大而增大.同时用微分脉冲伏安法对血红蛋白的催化反应条件进行了优化,选择了催化反应产物的伏安测定的最佳条件.在该条件下,该体系可用于血红蛋白的测定,线性范围为4.0×10-8～8.0×10-7mol/L,检出限为3.4 × 10-8 mol/L.用循环伏安法研究了该产物在不同pH B-R缓冲溶液中于玻碳电极上的电化学性质.     

Mn2+浓度对钒液流电池正极液的电化学性能影响

电解液中金属离子会影响钒液流电池的电化学性能。本文采用循环伏安法和电化学阻抗谱研究了正极液中Mn2+浓度对V髨/V(Ⅳ)电对的氧化还原过程影响规律,发现Mn2+在正极液中没有发生副反应,但严重影响V髨/V(Ⅳ)的反应活性、电极反应可逆性、离子扩散与电荷转移反应等电化学性能。循环伏安测试结果表明Mn2+浓度为0.04-0.13 g.L-1时,V髨/V(Ⅳ)电对电极反应可逆性和反应活性较高,钒离子扩散系数由参照溶液中的8.89×10-7-1.098×10-6增大至1.302×10-6-1.800×10-6 cm2.s-1,提高了-60%;电化学阻抗测试结果表明Mn2+浓度为0-0.04 g.L-1时,V髨/V(Ⅳ)电对电极反应阻抗和界面阻抗均较参照溶液中的增加不明显,但当Mn2+浓度增至0.07 g.L-1时,上述阻抗值较参照溶液增大了25%-28%。基于二者结果,Mn2+对电极反应有不同程度的负面影响,但是适当的Mn2+浓度有利于钒离子的扩散。     

The catalytic effect of bismuth for VO_2~+/VO~(2+) and V~(3+)/V~(2+) redox couples in vanadium flow batteries

The effect of bismuth(Bi) for both VO_2~+/VO2+ and V~(3+)/V~(2+) redox couples in vanadium flow batteries(VFBs) has been investigated by directly introducing Bi on the surface of carbon felt(CF).The results show that Bi has no catalytic effect for VO_2~+/VO2+ redox couple.During the first charge process,Bi is oxidized to Bi~(3+)(never return back to Bi metal in the subsequent cycles) due to the low standard redox potential of 0.308 V(vs.SHE) for Bi3+/Bi redox couple compared with VO_2+/VO2+ redox couple and Bi~(3+)exhibit no(or neglectable) electro-catalytic activity.Additionally,the relationship between Bi loading and electrochemical activity for V~(3+)/V~(2+) redox couple was studied in detail.2 wt%Bi-modified carbon felt(2%-BiCF) exhibits the highest electrochemical activity.Using it as negative electrode,a high energy efficiency(EE) of 79.0%can be achieved at a high current density of 160mA/cm~2,which is 5.5%higher than the pristine one.Moreover,the electrolyte utilization ratio is also increased by more than 30%.Even the cell operated at 140mA/cm2 for over 300 cycles,the EE can reach 80.9%without obvious fluctuation and attenuation,suggesting excellent catalytic activity and electrochemical stability in VFBs.     

直流偏压对于在玻碳电极上双层类脂膜成膜过程的影响

应用循环伏安法和电化学阻抗谱研究了直流偏压对卵磷脂在玻碳电极表面自组装成膜过程及其结构的影响.实验发现:无论在正偏压还是负偏压条件下,卵磷脂在玻碳电极上均可组装成膜.施加正偏压时,由于玻碳电极表面所带的正电荷与卵磷脂端基之间的静电作用,使得卵磷脂在电极表面倾向于形成双层的类脂膜,并在0.4V偏压下电极阻抗达到最大值.继续增大电极正向偏压,s-BLM缺陷增加,以至趋于被击穿.提出了适宜的等效电路,并据此非线性拟合电极过程,求得部分阻抗的模型参数.研究发现:膜电容和电荷传递电阻呈现良好的互补效应.     

Myoglobin on multi-walled carbon nanotubes modified electrode: direct electrochemistry and electrocatalysis

Electrochemical behavior of myoglobin (Myb) incorporated on multi-walled carbon nanotubes (MWNTs) modified GC electrode is investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The results indicate that Myb can be strongly adsorbed on the surface of the MWNT-modified electrode to form an approximate monolayer film. MWNTs can greatly promote the redox of horse heart Myb, on which a pair of well-defined and nearly reversible CV peaks for Myb Fe(III)/Fe(II) redox couple were obtained in pH 7.0 buffers. The formal potential of Myb on MWNT modified electrode shifts linearly with pH with a slope of −56.4 mV/pH, showing that the electron transfer is accompanied by single proton transportation. The high efficiency of the Myb/MWNT modified electrode towards the catalytic electro-reduction of nitric oxide has been observed. Potential application of Myb/MWNT modified electrode as biosensors to monitor NO is proposed.     

Synthesis of poly(3-methylthiophene) in the presence of 1-(2-Pyrrolyl)-2-(2-thienyl) ethylene by electropolymerization

In this study, the electropolymerization of 3-methylthiophene (3-MT) was preformed in the presence of a catalytic amount 1- (2-pyrrolyl)-2-(2-thienyl) ethylene (PTE) by cyclic voltammetry in acetonitrile as a solvent and lithium perchlorate as the electrolyte on a glassy carbon (GC) electrode. First, PTE was synthesized via the Wittig reaction. The addition of a catalytic amount of PTE during the electropolymerization of 3-MT changes the cyclic voltammograms such that the analysis of cyclic voltammograms of poly(3-MT) shows a considerable increase in the electroactivity and redoxability. Furthermore, the presence of PTE during the electropolymerization of 3-MT increases the polymerization rate. The CV measurement of the electron transfer ferro/ferricyanide redox system using different modified GC electrodes shows that the rate of charge transfer for poly(3-MT) in the presence of PTE is greater than that of poly(3-MT) alone. The conductivity of the obtained polymers was determined by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl (w/v) solutions. With the application of Zview(II) software to the EIS, we estimate the parameters of the proposed equivalent circuit, based on a physical model for the electrochemical behavior of coatings on the GC electrode, to be 15739 ohm cm² for the charge transfer resistance (R_ct) for poly(3-MT) alone and 9700 ohm cm² for poly(3-MT) in the presence of PTE. Thus, the film of poly(3-MT) formed in the presence of PTE is more conductive.     

Effect of oxygen-containing functional groups on the impedance behavior of activated carbon-based electric double-layer capacitors

The surface chemistry of activated carbon was treated with sulfuric acid and hydrogen to analyze the oxygen-containing functional groups on the impedance behavior of electric double-layer capacitors. Based on the electrochemical impedance spectrum (EIS), an equivalent circuit model was proposed considering the kinetic and charge transfer characteristics, and Marquardt fit procedure was applied to the EIS data. The simulated results indicate that the oxidation treatment made the ionic resistance within the pore of carbon electrode decrease, and the ion diffusion coefficients significantly increase, which leads to improvement of power capability of the carbon electrode.     

Electron-transfer studies in a lyotropic columnar hexagonal liquid crystalline medium

We have studied the electron-transfer properties of some redox systems on a gold electrode in a lyotropic hexagonal columnar liquid crystalline phase (H1 phase) using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The liquid crystalline medium consists of the nonionic surfactant Triton X-100 and water. The redox reactions that have been studied are ferrocene/ferricenium, [Fe(CN)6]3-/4-, and [Ru(NH3)6]3+/2+. We have confirmed by polarizing optical microscopy that the liquid crystalline nature of the medium is maintained even after the addition of the redox species and the supporting electrolyte. The CV studies show a significant shift in the half-peak potentials of these redox reactions in the liquid crystalline medium. From the EIS studies, we have measured the diffusion coefficients and the kinetic parameters for the redox species. These results are discussed and compared with the values obtained in the conventional solvent medium. The CV and impedance studies demonstrate that the hexagonal columnar phase provides a novel controlled environment for the study of electron-transfer reactions in biological and physiological media.     

Disposable electrochemical biosensor with multiwalled carbon nanotubes-chitosan composite layer for the detection of deep DNA damage.

A novel electrochemical DNA-based biosensor for the detection of deep DNA damage was designed employing the bionanocomposite layer of multiwalled carbon nanotubes (MWNT) in chitosan (CHIT) deposited on a screen printed carbon electrode (SPCE). The biocomponent represented by double-stranded (ds) herring sperm DNA was immobilized on this composite using layer-by-layer coverage to form a robust film. Individual and complex electrode modifiers are characterized by a differential pulse voltammetry (DPV) with the DNA redox marker [Co(phen)(3)](3+), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with [Fe(CN)(6)](3-) as a redox probe in a phosphate buffer solution (PBS). A good correlation between the CV and EIS parameters has been found, thus confirming a strong effect of MWNT on the enhancement of the electroconductivity of the electrode surface and that of CHIT on the MWNT distribution at the electrode surface. Differences between the CV and EIS signals of the electrodes without and with DNA are used to detect deep damage to DNA, advantageously using simple working procedures in the same experiment.     

Electrochemical impedance analysis of methanol oxidation on carbon nanotube-supported Pt and Pt-Ru nanoparticles

Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are employed to investigate methanol oxidation reactions on single-walled carbon nanotube-supported platinum (Pt) and platinum–ruthenium (Pt-Ru) nanoparticles. EIS and CV measurements show consistent results: Pt catalyst supported on single-walled carbon nanotubes possesses higher catalytic activity for methanol oxidation than that on carbon black. Additionally, semicircles in the second quadrant of the Nyquist diagrams are observed for methanol oxidation on all types of catalytic nanoparticles when applying an electrical potential of 600 mV, which indicates the occurrence of negative resistance during electrocatalytic methanol oxidations. However, all impedance spectra show positive resistance at other electrode potentials (e.g., 300, 400, and 800 mV). Electrocatalytic characteristics of all catalysts are further analyzed by equivalent circuit simulations. We propose that intermediate coverage on the catalyst surface and subsequently the oscillation of nonlinear electrochemical methanol oxidations lead to the occurrence of negative resistance at 600 mV.