银纳米修饰电极的制备及电化学行为

金属纳米粒子由于其小的体积和大的比表面积而具有独特的电子、光学和异相催化特性,是目前表面纳米工程及功能化纳米结构制备的一种理想研究对象[1]。银纳米粒子可广泛应用于催化剂材料、电池的电极材料、低温导热材料和导电材料等,成为近年来人们研究的热点[2,3]。在电化学方面,银纳米粒子具有比其他纳米粒子更为优异的导电性能和电催化性能。因此,研究银纳米粒子修饰电极有重要的应用价值和前景[4]。1实验部分1.1仪器CHI660电化学工作站(USA);TU-1901型双光束紫外可见分光光度计(北京普析通用仪器公司);KQ-100型超声清洗器(昆山市超声…     

Electrochemical Impedance Spectroscopic Investigation in Detecting 2,4‐dinitrophenylhydrazine Using Catalytic Effect of Copper at Glassy Electrode

This paper reports on the use of electrochemical impedance spectroscopy (EIS) allied to copper (II) for the determination of 2,4‐dinitrophenylhydrazine (DNPH) at glassy carbon electrode (GCE). The experiment measurements were carried out in methanol at a potential of 0.3 V versus Ag/AgCl. The Nyquist plots were modeled with a Randle equivalent circuit, by identifying the charge transfer resistance as the relevant concentration dependent parameter. These measurements show that the impedance spectra of DNPH increased by the formation of non‐electroactive compound produced from specific interaction between DNPH and Cu (II), which will block the electron‐transfer process of the redox probe. Therefore, the proposed methodology offers a detection limit of 4.0×10^?8 mol L^?1. The proposed methodology was satisfactorily applied to determine DNPH in industrial water samples.     

Direct and Simultaneous Determination of Phenol, Hydroquinone and Nitrophenol at Boron-Doped Diamond Film Electrode

The electrochemical characteristics of multi-component phenolic pollutants, such as phenol （Ph）, hydroquinone （HQ） and 4-nitrophenol （4-NP）, were investigated on boron-doped diamond （BDD） film electrode by differential pulse voltammetry （DPV） technique. A simple and feasible platform was accordingly established for the direct and simultaneous determination of these three phenolic pollutants. Results showed that, Ph, HQ and 4-NP gave obvious oxidation peaks on BDD electrode at the potential of 1.24, 0.76 and 1.52 V, respectively. Each of them displayed good linear relationship between their oxidation peak currents and their corresponding concentrations in a rather wide range coexisting with one or two of the other phenolic pollutants. The detection limits of Ph, HQ and 4-NP were estimated to be as low as 1.82×10^-6, 1.67×10^-6 and 1.44×10^-6 mol·L^-1, respectively. Therefore, a promising direct and simultaneous electrochemical determination method of multi-component phenolic pollutants in wastewater samples was constructed successfully on BDD electrode with advantages being rapid, simple, convenient, sensitive, in situ and inexpensive.     

Electroanalytical Determination of Morpholine as a Corrosion Inhibitor at a Cathodically Pretreated Boron-Doped Diamond Electrode

An electroanalytical method for the determination of morpholine, a corrosion inhibitor, was developed at a cathodically pretreated boron-doped diamond electrode (BDDE). The voltammetric response of morpholine at the BDDE in 0.1?mol L^?1 KCl (pH 10) shows an irreversible oxidation process at approximately 1.3?V vs. Ag/AgCl in 3.0?mol L^?1 KCl. Using cyclic voltammetry, the number of electrons involved in the morpholine electroxidation mechanism was found to be 1. The application of chronoamperometry showed that the apparent diffusion coefficient (D₀) was 2.99?×?10^?6 cm² s^?1. Using square wave voltammetry under the optimized conditions (frequency of 30.0?Hz, pulse amplitude of 100?mV and step potential of 20?mV at pH 10.0), the developed method provided limits of detection and quantification of 2.1 and 6.9?mg L^?1, respectively, with a linear range from 5.0 to 100.0?mg L^?1 (r?=?0.991). Intraday (n?=?10) and interday (two consecutive day) precision values assessed as the relative standard deviation for solutions containing 30.0, 60.0, and 90.0?mg L^?1 of morpholine were from 0.41 to 5.86% and 0.92 to 3.19%, respectively. The feasibility of the method for the interference-free determination of morpholine was verified by the analysis of synthetic boiler water samples containing CaCO₃, Na₂SO₃, Na₃PO_4, FeCl₃, and humic acid as organic matter. In addition, hydrazine was added as a possible interfering compound because of its widespread use in corrosion inhibition. Recovery values from 90.9 to 109.4% were obtained in the synthetic boiler water, thereby attesting to the accuracy of the method.     

碱性溶液中分子氧在多晶银上的多步还原

 Oxygen reduction on a polycrystalline silver electrode was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The reaction occurred by a two-electron pathway. The steps in the mechanism were observed in the cyclic voltammograms recorded with different scan rates. The intermediates formed in the steps were detected by electrochemical impedance spectroscopy.     

Voltammetric Behavior of Nitrofurazone at Highly Boron Doped Diamond Electrode

The electrochemical behavior of nitrofurazone (NFZ) at a highly boron doped diamond (BDD) electrode was studied in Britton‐Robinson (BR) buffer using cyclic voltammetry. NFZ was directly reduced to the amine derivative (RNH₂) in the pH range of 2.0 to 4.0 in a process involving six (6.0±0.4) electrons and six protons. In the range of pH 7.0 to 12 and, predominantly aqueous medium, the reduction step split into its two components: the reduction of NFZ to the radical anion (RNO₂^.?) and reduction of RNO₂^.? to hydroxylamine derivative (RNHOH) in processes involving one and three (3.1±0.1) electrons, respectively. On the anodic scan of the voltammograms and at pH 8.0, the oxidation of the hydroxylamine to the nitroso derivative (RNO), was observed in a process involving 2 (1.7±0.2) electrons and 2 protons. In addition and unreported in the literature on any electrode material, was the detection of a new oxidation peak at pH>8.0, which was observed regardless of whether NFZ had been previously reduced or not. The calculation of n, number of electrons, involved in each electrochemical step was satisfactorily accomplished using the Randles‐?evcik equation.     

SiO的电化学性能及其电极过程动力学研究

本文采用恒流充放电考察SiO的电化学性能，并在0.5 MHz至0.001 Hz的频率范围内，通过交流阻抗技术研究SiO电极在首次嵌锂反应中的电极过程。对不同电压区间下测得的交流阻抗图谱，提出不同的等效电路模型并对结果进行了拟合。通过拟合结果，探讨了SiO电极过程动力学以及嵌锂过程中电极界面的变化特性。     

Ti-V-Nb-Cr-Ni电极合金的微观结构及某些动力学性能研究

本文采用XRD，FESEM-EDS及电化学阻抗谱(EIS)等方法对V基固溶体Ti_0.25V_0.34Nb_0.01Cr_0.10Ni_0.30电极合金的微观结构及某些动力学性能，如交换电流密度(i₀)、氢的扩散系数(D)等进行了研究。XRD和FESEM-EDS分析测试结果表明：Ti_0.25V_0.34Nb_0.01Cr_0.10Ni_0.30电极合金由BCC结构的V基固溶体主相和少量的TiNi基第二相组成，其中，V基固溶体主相为树枝晶形状，TiNi基第二相呈网格状围绕着树枝晶。EIS及其等效电路分析结果表明，电极表面电化学反应的电荷转移电阻(R_T)随着温度的升高而降低，而交换电流密度和氢在合金本体中的扩散系数随着温度的升高而升高。在343 K时的交换电流密度分别为323 K和303 K的3.6倍和13.6倍，氢的扩散系数略有升高。电化学反应的表观活化能(Δ_rH)59.091 kJ·mol^-1远高于AB₅型合金的28.10 kJ·mol^-1。Ti_0.25V_0.34Nb_0.01Cr_0.10Ni_0.30合金电极的放电容量在303～343 K较宽的温度区间内随温度的升高而增加，且高温倍率放电(HRD)性能优于低温，当放电电流密度较大时，氢的扩散是放电过程的主要速度控制步骤。     

基于富勒烯衍生物修饰玻碳电极的DNA电化学传感器

以富勒烯C₆₀, L-苏氨酸及对苯二甲醛为原料, 在氮气保护下反应得到含醛基官能团的2-(4-醛基苯基)-5-(1-羟乙基)富勒烯吡咯烷衍生物(C₆₀-CHO). 将该材料修饰于玻碳电极表面, 并利用醛基与氨基之间温和、高效的缩合反应, 将5-氨基修饰的寡聚核苷酸共价固定到了C₆₀-CHO修饰的玻碳电极表面, 构建了一种新型的电化学DNA传感器. 以[Fe(CN)₆]^3−/4−为电活性探针, 采用电化学阻抗法对转基因植物CaMV35S启动子基因特征片段进行检测. 实验结果表明, 杂交前后的电子传递电阻差值(DR_et)与目标序列浓度对数(lg C_S2)在1.0×10^－13～1.0×10^－9 mol/L浓度范围内呈良好的线性关系, 线性回归方程为DR_et/(10³ Ω)＝3.471 lg (C_S2/mol/L)＋50.425 (r＝0.9977), 检测限为1.5×10⁻¹⁴ mol/L. 杂交特异性实验进一步表明该传感器对完全互补、碱基错配和非互补序列具有良好的识别能力.     

A Highly Sensitive Electrochemical Impedance Spectroscopy Immunosensor for Determination of 1‐Pyrenebutyric Acid Based on the Bifunctionality of Nafion/Gold Nanoparticles Composite Electrode

A simple, highly sensitive and label‐free electrochemical impedance spectroscopy (EIS) immunosensor was developed using Nafion and gold nanoparticles (nano‐Au/Nafion) composites for the determination of 1‐pyrenebutyric acid (PBA). Under the optimal conditions, the amount of immobilized antibody was significantly improved on the nano‐Au/Nafion electrode due to the synergistic effect and biocompatibility of Nafion film and gold nanoparticles composites. The results showed that the sensitivity and stability of nano‐Au/Nafion composite electrode for PBA detection were much better than those of nano‐Au modified glassy carbon electrode (nano‐Au/GCE). The plot of increased electron transfer resistances (R_ets) against the logarithm of PBA concentration is linear over the range from 0.1 to 150 ng·mL^?1 with the detection limit of 0.03 ng·mL^?1. The selectivity and accuracy of the proposed EIS immunosensor were evaluated with satisfactory results.     

Electrochemical Impedance Spectroscopic Measurements of Sexithiophene—Effect of the Electrode Nature and the Dopant (CuCl2) Content

Electrochemical impedance spectroscopic (EIS) measurements of sexithiophene (6T) were carried out according to the Pt/6T/M sandwich structure configuration, for various electrode materials (M＝GC, ITO, Ag, Cu, Al) and for different doping levels of copper chloride (CuCl2). The results demonstrate that two types of charge transport are involved in the redox process at the electrode/6T interface and inside the bulk oligomer. The complex-plane impedance plots obtained for various doping levels of CuCl2 exhibit arc shapes. The charge-transfer resistance measured from the diagrams decreases systematically with the addition of the salt, leading to an increase of the oligothiophene conductivity.     

硼掺杂金刚石薄膜电极上二氯酚的电化学阻抗谱研究

以2,4-二氯酚(2,4-DCP)和2,6-二氯酚(2,6-DCP)为模型污染物,采用循环伏安法和电化学阻抗谱研究了硼掺杂金刚石(BDD)电极上2种氯酚的电催化氧化过程.结果表明,2,4-DCP和2,6-DCP的氧化电位分别为1.55和1.62 V.等效电路拟合结果表明,当极化电位由开路电位提高至1.5 V时,2种氯酚的电荷转移电阻均有明显下降,反应控制步骤为扩散控制步骤.与2,6-DCP相比,2,4-DCP在BDD电极上更容易发生直接电化学氧化.     

Synthetic Semiconductor Diamond Electrodes: Electrochemical Characteristics of Homoepitaxial Boron-doped Films Grown at the (111), (110), and (100) Faces of Diamond Crystals

Electrode behavior of homoepitaxial (single-crystal) boron-doped diamond films deposited onto differently orientated faces of dielectric diamond single crystals is studied by the electrochemical impedance and potentiodynamic curve methods. It is shown that the acceptor concentration determined from the slope of Mott–Schottky plots decreases, in the epitaxial films grown under the same conditions, in the series: (111) > (110) > (100). This is explained by different intensity of boron incorporation, from gas phase, into differently orientated faces of the diamond crystals during their growth. The rate of electrode reactions in the Fe(CN)₆ ^3–/4– and Ru(NH₃)₆ ^2+/3+ redox systems decreases in the above series, which obeys the earlier found interrelationship between the electrochemical kinetics at diamond electrodes and their doping level.     

Si／C复合材料电极首次嵌锂过程的电化学阻抗谱研究

采用球磨法制备了Si／C复合材料,X射线衍射（XRD）和扫描电子显微镜（SEM）测试结果显示Si／C复合材料中硅保持着良好的晶体结构且均匀的分散于炭黑基体中．充放电测试结果表明Si／C复合材料首次放电容量高达3393mAh／g,4周之后可逆容量均保持在1000mAh／g左右,表现出较好的循环性能．电化学阻抗谱测试结果显...     

三维多孔Sn-Co合金负极制备及其电化学性能研究

采用化学镀方法制备三维多孔铜.以其作为集流体,借助电沉积制备三维多孔Sn-Co合金电极.X-射线衍射(XRD),扫描电镜(SEM)分析表明,以多孔铜为集流体制备的SnCo合金电极主要存在CoSn2相和纯Sn相,为三维多孔结构.充放电结果显示,三维结构SnCo合金电极比平面铜集流体上镀得的SnCo合金电极表现出更优越的充放电性能.前者的首次放电(嵌锂)容量为636.3mAh/g,充电(脱锂)容量为528.7mAh/g,首次库仑效率为83.1%,70周后容量为529.5mAh·g-1,保持率为82.6%.此外,还应用电化学阻抗初步研究了三维Sn-Co合金电极在充放电过程发生的嵌脱锂过程.     

Electroanalytical Characteristics of Lercanidipine and its Voltammetric Determination in Pharmaceuticals and Human Serum on Boron-Doped Diamond Electrode

The electrooxidative behavior and determination of lercanidipine (LRC) were investigated in aqueous acetonitrile medium at a boron-doped diamond electrode using voltammetric techniques. The LRC in selected supporting electrolyte presents a well-defined anodic response at 0.944 V, studied by the proposed method. The linear response was obtained in the ranges of 4 × 10^?6 to 2 × 10^?4 mmol L^?1 range in 0.5 mmol L^?1 sulfuric acid supporting electrolyte and 1 × 10^?5 to 8 × 10^?5 mmol L^?1 range in spiked serum sample for square wave voltammetric technique. No electroactive interferences from the excipients and endogenous substances were found in the pharmaceutical dosage form and in the biological sample, respectively.     

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.     

Polyfurfural-Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode for the Direct Determination of Nitrofurazone

An electrochemical sensor based on a polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode has been developed for the sensitive and rapid determination of nitrofurazone. The morphologies and properties of the sensor were characterized by electrochemical impedance spectroscopy, scanning electron microscopy, cyclic voltammetry, and differential pulse voltammetry (DPV). In pH 7.0 Britton–Robinson buffer solution, the as-prepared polyfurfural-electrochemically reduced graphene oxide modified glassy carbon electrode shows excellent electrocatalytic performance for the electrochemical reduction of nitrofurazone, and the reduction peak current is about 9.45, 1.31, and 1.25 times higher than that of the bare glassy carbon electrode, polyfurfural modified glassy carbon electrode, and electrochemically reduced graphene oxide modified glassy carbon electrode, respectively. The DPV determination of nitrofurazone indicates that the linear range and detection limit of nitrofurazone are 1–50 and 0.25?µmol/dm³, respectively. In addition, this sensor exhibits high selectivity, reproducibility, stability, and also was successfully used to directly determine nitrofurazone in the commercial antibacterial lotion with comparative sensitivity to high-performance liquid chromatography, showing its promising application prospects.     

Electrochemical Behavior of a Gold Electrode Modified with SWNTs/DDAB Films and Its Electrocatalytic Activity Towards Ascorbic Acid

A film of single-wall carbon nanotubes (SWNTs) and didodecyldimethylammonium bromide (DDAB) is prepared by casting a solution of SWNTs and DDAB onto the surface of a gold electrode. The electrochemical behavior of the film is investigated by electrochemical impedance spectroscopy and cyclic voltammetry. In a 0.10 M phosphate buffer solution of pH 7.0, the film-modified electrode gives a pair of redox peaks in cyclic voltamograms, with the anodic and cathodic peak potentials of 0.095 and 0.042 V. The peak currents change linearly with the scan rate at 30–500 mV/s. The modified electrode has an excellent electrocatalytic activity towards the oxidation of ascorbic acid (AA). The catalysis currents are proportional to the AA concentration in the range of 5.0 × 10⁻⁴ to 3.2 × 10⁻² M. The linear-regression equation is i (μA) = 1.2079 + 1.3987 × 10³ c _AA (M), with a correlation coefficient of 0.9995. The detection limit is 2.2 × 10⁻⁴ M (signal-to-noise ratio of 3). The Michaelis-Menten constant (K _m) is 1.0 × 10⁻⁴ M by the Lineweaver-Burk equation. __________ From Elektrokhimiya, Vol. 41, No. 10, 2005, pp. 1193–1199. Original English Text Copyright ? 2005 by Cheng, Jin, Zhang. The text was submitted by the authors in English.     

基于对羟基苯硼酸为前驱体的金纳米粒子修饰电极电化学检测过氧化氢

以对羟基苯硼酸为前驱体,利用H₂O₂可以定量氧化对羟基苯硼酸产生对羟基苯酚的原理,以反应产物对羟基苯酚为电化学信号物质,结合金纳米粒子修饰玻碳电极（AuNPs/GCE）,发展了一种间接检测H₂O₂的电化学方法. 由于AuNPs/GCE具有有效电子传递性能和比表面积大等优点,对硼酸氧化产物具有较高的催化活性,因此在含1.0 mmol•L^-1对羟基苯硼酸的0.1mol•L^-1 pH 7.5 PBS中,AuNPs/GCE可以检测到1.0 ~ 1.0 × 10³ μmol•L^-1的H₂O₂,检测限为0.5μmol•L^-1. 同时,该方法具有良好的选择性和重现性,且操作简单、速度快、价格低廉,非常适用于实际样品中H₂O₂含量的测定.