普鲁士蓝膜的电沉积及其电化学阻抗谱

利用循环伏安法在两种不同组成的电解液中进行铂电极上普鲁士蓝膜的电化学沉积，在氯化钾溶液中测量了修饰膜的循环伏安行为，比较了两种膜的电化学阻抗谱。修饰普鲁士蓝膜铂电极的电化学阻抗谱测量结果表明，沉积条件及其沉积膜厚度均对电子传递过程产生影响。     

普鲁士蓝膜修饰铂电极的现场拉曼光谱电化学表征(英文)

采用现场拉曼光谱电化学技术表征了普鲁士蓝膜修饰铂电极的循环伏安过程 .结果显示 ,随着修饰膜的微观结构由普鲁士蓝向普鲁士白或相反过程转化 ,表征两种不同结构的拉曼特征振动谱峰及其强度变化呈现出明显的可逆特征 .     

对苯二酚在掺Cu(Ⅱ)类普鲁士蓝膜修饰电极上的电化学行为研究

采用循环伏安法在普鲁士蓝膜中掺杂Cu2+,制得掺Cu(Ⅱ)类普鲁士蓝膜(Cu-PB膜)。利用循环伏安法、库仑分析法和电化学阻抗法对Cu-PB膜进行电化学表征,结果显示Cu2+进入普鲁士蓝的内部结构,取代了其中的高自旋铁。该Cu(Ⅱ)类普鲁士蓝膜对对苯二酚具有明显的电催化作用,电极反应过程是扩散控制的准可逆过程,在5.0×10-5~1.0×10-3mol.L-1范围内,还原峰电流与对苯二酚浓度呈良好的线性关系,检出限为1.0×10-6mol.L-1。计算了对苯二酚在Cu-PB膜修饰电极上电极过程的动力学参数。     

循环伏安和现场红外光谱电化学研究镉(Ⅱ)在普鲁士蓝/铂修饰电极上的反应

报道了普鲁士蓝(PB)膜修饰Pt电极在CdCl_2溶液中进行循环伏安(CV)扫描,衍生为含有部分六氰亚铁酸镉(CdHCF)混合修饰膜的电化学反应,并对其反应机理进行了电化学和现场红外光谱电化学(FTIRs)的研究.实验结果表明,这一混合膜中PB和CdHCF两种成分之间的相互影响并不大,两种物质基本上保持了各自为纯物质时的电化学特性.     

普鲁士蓝膜修饰电极循环伏安行为的研究

本文研究普鲁士蓝(PB)膜修饰电极的循环伏安行为,结果表明,膜中电活性中心间的相互作用导致PB膜电极的伏安行为偏离理想表面波.用有限扩散边界模型解释了高电位扫速下膜电极的伏安行为.在含钾离子的电解质溶液中测得PB膜中电荷传输扩散系数为10~(-9)～10~(-11)cm~2/s.     

金属间化合物LaCo13的电化学储氢性能研究

研究了金属间化合物LaCo13的电化学储氢性能,分别考察了LaCo13电极的活化、电化学容量、温度特性、电位特性、循环寿命和高倍率放电性能,并采用电化学阻抗谱技术研究了LaCo13电极过程的动力学性能.结果表明,LaCo13在电解液中具有较高的电化学容量和良好的循环寿命,温度由30℃升高到60℃时,LaCo13电极的电化学容量从339升高到388 mAh·g-1,但放电平台压较低,高倍率放电性能不如AB5型合金.LaCo13电极过程动力学性能表明,其吸放氢是由电化学反应和氢的扩散混合控制.     

对苯二酚在普鲁士蓝修饰电极上的电化学行为

利用循环伏安法制备普鲁士蓝修饰玻碳电极(PB/GC),电极对对苯二酚具有良好的电催化作用,PB/GC电极上的氧化还原峰电流比裸电极大两个数量级,峰电位之差从0.83V减少到0.48V;考察了修饰电极膜的厚度与峰电流关系,当扫描圈数大于60圈时,峰电流不再随着薄膜厚度的增加而变大,峰电流与扫描速度的平方根呈线性关系,说明膜电极在界面传质为线性扩散控制;采用计时电量和电化学阻抗法研究对苯二酚的电化学行为,求得在不同厚度修饰电极膜上的扩散系数,此电极可用来快速检测对苯二酚。     

普鲁士蓝膜修饰极循环伏安行为的研究

本文研究普鲁士蓝（PB）膜修饰电极的循环伏安行为，结果表明，膜中电活性中心间的相经作用导致PB膜电极的伏安行为偏离理想表面波，用有限扩散边模型解释了高电位扫速下膜电极的伏安行为，在含钾离子的电解质溶液中测得PB膜中电荷传输扩散系数为10^-9-10^-11cm^2/s。     

酸性溶液中硝基苯在WC电极上的电化学还原

以聚四氟乙烯为粘接剂制成碳化钨(WC)电极.采用循环伏安法、线性扫描法和恒电位阶跃法研究了硝基苯在酸性溶液中WC电极上的电化学行为.实验表明:WC电极对硝基苯的还原具有较好的活性,电极过程受扩散和电化学步骤混合控制;表观活化能为23.7kJ·mol 1,其中,电化学步骤的活化能10.91kJ·mol 1.     

电化学石英晶体微天平研究普鲁士蓝薄膜的两电极系统伏安行为

采用双通道电化学石英晶体微天平（EQCM）研究了水溶液中普鲁士蓝（PB）薄膜修饰的两金电极上的两电极循环伏安（CV）电化学行为,归属了普鲁士白、PB、普鲁士黄三者间的转变过程,以及金基底和PB膜内所夹带的Fe（CN）6^3-／Fe（CN）6^4-杂质的氧化还原峰,为UV-Vis光谱电化学实验所支持．夹在两喷金的铟锡氧化物（ITO）电极间的PB粉末的两电极固态CV图和两PB修饰金电极在水溶液中的两电极CV图相似,说明发生了类似的电极反应．双通道EQCM有望成为研究其他物质或材料的两电极系统电化学行为的高效技术．     

抗坏血酸在普鲁士蓝薄膜修饰电极上的电催化氧化

本文详细研究了普鲁士蓝(PB)薄膜本身电荷传输过程的动力学及PB 薄膜催化抗坏血酸(AH2)电氧化的动力学。 用电位阶跃计时电流法和计时电量法, 恒电流计时电位法测得PB膜中电荷传输表观扩散系数Dct平均为2.62×10ˉ10cm2·sˉ1; 用RDE法测得AH2在PB薄膜上催化氧化的速率常数为1.23×10^8cm3·molˉ1·sˉ1。催化反应对AH2为一级。 只发生在PB薄膜与溶液的界面上。 整个催化过程受到溶液中的传质、膜内部的电荷传输及膜与溶液界面上交叉反应三种因素单独或联合控制, 实际出现四种动力学情况。     

Electrochemical characteristics of poly(ophenylendiamine) film electrodes in phosphatic solution

The electrochemical characteristics of poly(o-phenylendiamine) (POPD) film modified electrodes have been investigated using different electrochemical techniques.The main interest is focused on the effect of potential and film thickness on the electrode process.Good agreement has been found for the apparent diffusion coefficient estimated by chronocoulometry and impedance spec-troscopy.The charge transfer process within POPD films is diffusion processes at negative and positive overpotentials and electron hopping mechanism at formal potential.The POPD film conductivity of the oxidized state is better than that of the reduced state.For all electrode processes,the H+ may penetrate the film/electrolyte interface and take part in charge transfer or protonation-deprotonation of phenazine rings.     

聚阿魏酸修饰电极的电化学特性及电催化性能

研究了阿魏酸在玻碳电极表面电聚合成膜的方法和条件,测量了应用电化学方法制备不同厚度的阿魏酸修饰电极的循环伏安行为及其它电化学性质.对厚度为0.5 μm的阿魏酸膜,测得的电子转移系数为0.49,表观电极反应速率常数(ks)为6.56 s－1.扩散系数DR为7.9×108 cm2•s－1,Do为4.48×108 cm2•s－1.该修饰电极对烟酰胺腺嘌呤二核苷酸（NADH）氧化具有很好的催化作用.NADH浓度在0.01～5.0 mmol•dm－3范围内与峰电流呈现良好的线性关系.     

Study on the Impedance Characteristic and Electrocatalytic Activity of Platinum‐Modified Polyaniline Film

The composite electrode of platinum‐modified polyaniline film is formed in 0.5 M H₂SO₄ + 3 mM H₂PtCl₆ solution by cyclic potential or constant potential deposition of platinum particles in polyaniline film. To make a comparison, the polyaniline film with the same initial thickness and structure is also treated with the cyclic potential or constant potential polarization in 0.5 M H₂SO₄ solution. The electrochemical impedance spectroscopy (EIS) of the composite electrode of platinum‐modified polyaniline film is studied in sulfuric acid solution and compared with the EIS of the polyaniline film without platinum dispersion. The results show that the different modes of potential polarization affect greatly the nature and distribution of the platinum particles, instead of the structure of the polyaniline film (matrix). The electrode reaction kinetics and mass transport process parameters involving charge transfer resistance (R_ct), double layer capacitance (C_dl), constant phase elements (CPE) and Warburg impedance in platinum substrate/platinum‐modified polyaniline film/solution interface are discussed on the basis of the interpretation of the characteristic impedance spectra and connected to the electrocatalytic activity on the oxidation of methanol molecules.     

Effect of electrolyte cations on the charge transfer in films of prussian blue

Charge transfer in films of Prussian blue is studied by cyclic voltammetry and chronoamperometry at potentials of first (PB/PW) and second (PB/PY) redox processes in solutions of potassium, cesium, and ammonium nitrates (pH 4.0). The current relaxation following a film perturbation by a small-amplitude voltage pulse is analyzed with theoretical relationships obtained earlier for the charge transfer in redox polymers. Parameters, characterizing the charge transfer rate (formal diffusion coefficient, instantaneous current), are calculated and analyzed as a function of the film oxidation state and the supporting-electrolyte nature     

血红蛋白在壳聚糖修饰碳纳米管上的电化学特性及对过氧化氢的电催化分析

用壳聚糖对多壁碳纳米管进行修饰,构建了一种用于固定血红蛋白的新型复合材料,并研究了血红蛋白在该碳纳米管上的电化学性质及其对过氧化氢的电催化活性.扫描电镜结果表明,壳聚糖修饰的多壁碳纳米管呈单一的纳米管状,并能均匀分散在玻碳电极表面.紫外光谱分析表明血红蛋白在该复合膜内能很好地保持其原有的二级结构.将该材料固定在玻碳电极上后,血红蛋白能成功地实现其直接电化学.根据峰电位差随着扫描的变化,计算得到血红蛋白在壳聚糖修饰的碳纳米管膜上的电荷转移系数为0.57,表观电子转移速率常数为7.02 s-1.同时,该电极对过氧化氢显示出良好的催化性能,电流响应信号与H2O2浓度在1.0×10-6 ～1.5×10-3 mol/L间呈线性关系,检出限为5.0×10-7 mol/L.修饰电极显示了良好的稳定性.     

Electrochemical impedance studies of the undoping process of platinum phthalocyanine charge transfer microcrystals

Platinum phthalocyanine (PtPc) microcrystal films undergo three successive electrochemical oxidations. Each of these processes is associated with anion insertion or doping. The reverse process of anion insertion, undoping, has been investigated using electrochemical impedance spectroscopy and in-situ UV–vis spectroscopy. The impedance theory of conductive polymer films developed by Vorotyntsev et al. is applicable to this process. The kinetics of the undoping process depend upon the previous oxidative treatment, and thus the doping level. Three different states of the film can be demarcated, depending on the degree of oxidation (and thus the degree of doping) of the PtPc film. These are called the lightly doped, the conductive and the over-doped state, respectively. For lightly doped films, the film conductivity, the redox capacitance, the diffusion coefficient for charge transport and the rate of electrochemical reaction all decrease with decreasing potential. The film conductivity depends upon the concentration of free charge carriers. For the more highly doped conductive film, all of the above parameters are greatly enhanced, and the electrochemical reaction is accelerated and proceeds at a very high rate. The potential dependence of the redox capacitance and the diffusion coefficient depends on the type of anion. During undoping at 0 V, unusually high diffusion coefficients with a magnitude of order 10⁻² cm² s⁻¹ are observed and are attributed to the strong interactions between the electronic and ionic carriers during the phase transformation. For the over-doped film, undoping leads to an increase in the film conductivity and electrochemical reaction rate. The potential dependence of the redox capacitance and diffusion coefficients for charge transport implies strong interactions within the film. Hypsochromic shifts in UV–vis spectra with decreasing potential indicate conformational relaxation during the undoping process. SEM investigation confirms that the doped film swells during the de-doping process.     

血红蛋白在离子液体[BMIM]PF6碳糊电极上的直接电化学

制备了离子液体[BMIM]PF6修饰碳糊电极(CILE), 并对其形貌和电化学行为进行了表征. 采用涂布法利用壳聚糖-皂土有机-无机复合膜将血红蛋白(Hb)固定于CILE电极表面, 利用紫外可见光谱、红外光谱和电化学方法等手段对包埋于膜内的Hb的性质进行了表征. 结果表明, Hb在薄膜内保持了其原始构象与生物活性, 循环伏安实验表明, 在pH=7.0的Britton-Robinson (B-R)缓冲液中, Hb表现出一对峰形良好的准可逆氧化还原峰, 为Hb Fe(III)/Fe(II)电对的特征峰, 对其直接电化学行为进行了研究, 求出式电位为-0.352 V(vs SCE), 电子转移数为0.885, 电荷传递系数为0.578, 表观异相电子转移速率常数为0.149 s-1.     

Influence of copper hexacyanoferrate film thickness on the electrochemical properties of self-assembled 3-mercaptopropyl gold electrode and application as a hydrazine sensor

A copper hexacyanoferrate film was obtained on a modified electrode prepared by self-assembly of 3-mercaptopropyltrimethoxysilane on a gold surface. The film thickness was controlled using a layer-by-layer technique to tune the electrocatalytic properties of the electrode. Two electrodes with different hexacyanoferrate film thicknesses were prepared via three immersions (AuS/CuHCF3) and six immersions (AuS/CuHCF6) of the film in the precursor solutions. Cyclic voltammetry data were obtained to determine the adequate film thickness. Scanning electron microscopy images showed a roughness increase due to the growth of the film thickness at the electrode surface. Electrochemical impedance spectroscopy showed distinct behavior for the two electrodes prepared; while diffusion and charge transfer processes can be observed in both electrodes, an additional capacitive process at intermediary frequencies was observed for the AuS/CuHCF6 electrode. The charge transfer resistance (R _ct) for the AuS/CuHCF3 electrode (19.6 Ω cm²) was lower than for AuS/CuHCF6 (27.9 Ω cm²) due to the hexacyanoferrate film thickness, since the charge transfer process demands the simultaneous diffusion of K⁺ into the surface. Cyclic voltammetry was used to evaluate the application of the AuS/CuHCF3 electrode as an electrochemical sensor, revealing a linear correlation for hydrazine concentrations.     

Application of 2-(3,4-dihydroxyphenyl)-1,3-dithialone self-assembled monolayer on gold electrode as a nanosensor for electrocatalytic determination of dopamine and uric acid

The electrooxidation of dopamine (DA), uric acid (UA) and their mixture on a gold electrode modified by a self-assembled monolayer of 2-(3,4-dihydroxyphenyl)-1,3-dithialone has been studied by cyclic voltammetry (CV), chronoamperometry and differential pulse voltammetry (DPV). CV was used to investigate the redox properties of the modified electrode at various scan rates and the apparent charge transfer rate constant (k(s)), and transfer coefficient (α) were calculated. The mediated oxidation of DA at the modified electrode under the optimum condition (pH = 7.0) in CV occurs at a potential about 220 mV less positive than that of the unmodified gold electrode. The values of electron transfer coefficients (α), catalytic rate constant (k) and diffusion coefficient (D) were calculated for DA, using electrochemical methods. DPV exhibited a linear dynamic range over the concentration range of 0.2-250.0 μM and a detection limit (3σ) of 0.07 μM for DA. The modified electrode was used for simultaneous determination of DA and UA by DPV. The results showed that the electrode is highly efficient for the catalytic electrooxidation of DA and UA, leading to a remarkable peak resolution (~350 mV) for two compounds. The electrode was used for the determination of DA in an injection sample.