抗坏血酸在铂纳米粒子/碳纳米管/聚吡咯复合修饰电极上的电化学行为

研究了抗坏血酸在铂纳米粒子/碳纳米管/聚吡咯复合膜修饰电极上的电化学行为,发现复合修饰电极对抗坏血酸的电化学反应具有较好的电催化作用,与空白电极相比电化学氧化电流增加了7倍。用电化学阻抗谱研究了电子在修饰电极界面上的传输过程,发现修饰电极的电催化性能与修饰电极可以提高界面电子传输能力是相关的。同时研究了碳纳米管用量、支持电解质、扫速、电沉积条件等因素对抗坏血酸在修饰电极上电化学行为的影响。     

抗坏血酸在PPy-HEImTfa/Pt电极上的电催化氧化及其机理

以铂为基底电极,在1-乙基咪唑三氟乙酸盐(HEImTfa)离子液体中电化学合成导电聚吡咯(PPy),制得PPy-HEImTfa/Pt电极;采用循环伏安法研究了PPy-HEImTfa/Pt电极对抗坏血酸的电催化氧化性能.结果表明:PPy-HEImTfa/Pt电极对0.1mo·lL-1抗坏血酸具有较高的电催化氧化活性,与相同条件下硫酸溶液中在铂表面修饰的聚吡咯(PPy-H2SO4/Pt)电极和裸铂电极相比,其氧化峰电位分别降低了0.10和0.19V,氧化峰电流分别增加了3.0和3.6mA.同时采用原位傅里叶变换红外(insitu FTIR)光谱技术对抗坏血酸在PPy-HEImTfa/Pt电极上的电氧化机理进行了研究,结果表明:抗坏血酸在PPy-HEImTfa/Pt电极上首先被氧化为脱氢抗坏血酸,在水溶液中脱氢抗坏血酸迅速发生水合作用形成水合脱氢抗坏血酸,它进一步水解并发生内酯开环反应生成2,3-二酮古洛糖酸;在较高电位下,部分抗坏血酸最终被氧化成CO2.     

聚苯胺薄膜修饰电极对抗坏血酸的电催化氧化

本文表明聚苯胺(PAn)薄膜修饰电极对水溶液中的抗坏血酸(AH_2)在较宽的pH范围和较宽的浓度范围内均有良好的电催化氧化作用, 为EC平行催化过程。利用旋转圆盘电极(RDE)进行了催化过程动力学分析, 求出了催化反应动力学参数。在抗坏血酸浓度10~(-2)～10~(-6) mol·L~(-1)范围内, 催化峰电流与AH_2浓度均成良好的线性关系, 且PAn薄膜修饰电极具有很好的稳定性, 有应用分析抗坏血酸的意义。     

抗坏血酸在离子液体修饰玻碳电极上的电化学行为

利用离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)对玻碳电极(GCE)进行修饰,制备了BMI-MBF4/GCE电极.在0.1mol/L的磷酸盐缓冲溶液中,采用循环伏安法研究了抗坏血酸在BMIMBF4/GCE电极和裸玻碳电极(GCE)上的电化学行为.结果表明,pH=5.7的磷酸盐缓冲溶液为最佳测定底液,最佳富集时间为120s;BMIMBF4/GCE对抗坏血酸的氧化反应有很好的电化学催化作用.抗坏血酸的氧化峰电流与其浓度在2.0×10-4～1.0×10-2 mol/L的范围内呈良好的线性关系,相对标准偏差为4.53%(n=5).     

V(IV)在不同电极上氧化还原动力学研究

分别以导电塑料集流板、石墨棒、铂片作工作电极,应用循环伏安法和稳态极化法研究V(IV)的阳极氧化动力学过程,计算V(IV)在不同材料电极上的反应动力学参数.结果表明,以导电塑料板作电极,硫酸氧钒有较宽的水稳定区,且析氧电位较高;在石墨电极上,V(V)/V(IV)的交换电流密度较大,表现出较好的可逆性;而在铂电极上,硫酸氧钒更易析氢.     

Determination of Ascorbic Acid by a Composite-Modified Platinum Electrode

Thin composite layers of poly(3,4-ethylenedioxythiophene) and poly(4-lithium styrene sulfonic acid) were formed on a platinum surface. The modified electrode platinum/polyethylenedioxythiophene:poly(4-lithium styrene sulfonic acid) was characterized by cyclic voltammetry, chronocoulometry, and electrochemical impedance spectroscopy. The results showed that the electrode may be used as a working electrode for electroanalytical methods. This electrode was used for the determination of ascorbic acid. The effect of composite layer thickness on the functionality of the electrode was characterized for ascorbic acid determination. Another investigated aspect was the process of ascorbic acid oxidation in solutions of various pH values. The results showed that the modified electrode was suitable for the determination of ascorbic acid in various electrolytes from pH 2 to 7.6 in the presence and absence of buffer solutions. The linear dynamic range of ascorbic acid concentrations corresponded to its concentrations in physiological fluids.     

一氧化氮在Nafion-钴席夫碱膜修饰电极上的电催化氧化及其测定

将一种杂环席夫碱N,N′-2 ,6 -二乙酰吡啶缩双苯胺和Nafion修饰在铂电极上 ,然后与钴 (Ⅱ )反应 ,得到Nafion -钴席夫碱膜修饰电极。实验结果表明 ,该修饰电极具有良好的机械、化学和电化学稳定性 ,对生物分子一氧化氮的电化学氧化有显著的催化作用。以1.5次微分线性扫描伏安法测定一氧化氮 ,当浓度在2.8×10-6～8.4×10-8 mol/L范围时 ,氧化电流与浓度有良好的线性关系 ,抗坏血酸、精氨酸及亚硝酸根不干扰测定。     

聚苯胺纳米纤维修饰石墨箔电极的制备及电化学性能

以石墨箔(GF)为工作电极, 采用循环伏安法(CV), 通过电化学聚合, 制备了聚苯胺(PANI)纳米纤维修饰GF电极(Nano-PANI/GF). 利用红外光谱(FTIR)研究了Nano-PANI/GF修饰电极上聚合物的组成, 利用扫描电镜(SEM)观测了Nano-PANI/GF修饰电极的表面形貌. 利用循环伏安法研究了Nano-PANI/GF修饰电极在0.1 mol/L磷酸盐缓冲溶液(pH=6.9)中的电化学活性, 发现Nano-PANI/GF修饰电极在中性溶液中有良好的电化学活性. Nano-PANI/GF修饰电极对抗坏血酸(AA)电化学氧化的催化作用结果表明, 在0.2 V(vs. SCE)电位下, 在浓度范围1.7~2.0×10³ μmol/L内, 抗坏血酸的氧化电流与浓度呈良好线性关系, 线性方程式为y=0.00013x+0.0031. 修饰电极对抗坏血酸的最低检测限为1.7 μmol/L(S/N=3).     

同时测定多巴胺和肾上腺素的大环镍膜修饰电极

研究了大环镍膜修饰电极对多巴胺和肾上腺素的电化学响应特性；结果表明，该修饰电极对多巴胺和肾上腺素的电极反应具有良好的催化活性，多巴胺和肾上腺素在修饰电极上的氧化电位比在裸铂电极上分别负移了230mV和70mV，使二者的阳极峰得到很好的分离，且灵敏度大为提高；将该修饰电极用于多巴胺和肾上腺素的同时检测，获得满意结果，生物体中的主要干扰物质抗坏血酸和NO2^-等均不干扰测定。     

Electrochemical synthesis of self-doped polyaniline and its use to the electrooxidation of ascorbic acid

Self-doped polyaniline (PAN) film on platinum electrode surface has been synthesized via electrochemical copolymerization of aniline with orthanilic acid (OAA). Fourier transform infrared, UV–Vis, and elemental analysis indicate the formation of the copolymer and that the copolymer has the structure of a head-to-tail coupling of aniline and OAA units. It was found that the internal doping of PAN with OAA can extend the electroactivity of PAN in neutral and even in alkaline media. The obtained self-doped PAN (PAN-OAA)-coated platinum electrode is shown to be a good surface for the electrooxidation of ascorbic acid (AA) in phosphate buffer solution of pH 7. The anode peak potential of AA shifts from 0.63 V at bare platinum electrode to 0.34 V at the PAN-OAA-modified platinum electrode with greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5–60 mM using cyclic voltammetry. Rotating disk electrode voltammetry and chronoamperometry have been employed to investigate the electrooxidation of AA. The PAN-OAA-modified platinum electrode shows good stability and reproducibility.     

新型聚邻苯二酚/铂复合膜修饰电极对甲醛电化学氧化

研究了聚邻苯二酚／铂复合膜（Pt／polymer／GC）修饰电极对甲醛的催化氧化作用。结果表明,甲醛在Pt／polymer／GC电极上的氧化过程是一表面控制过程。电解质体系对甲醛的催化氧化有明显影响：在0．5mol／L硫酸中,甲醛主要发生第一步氧化生成甲酸的反应。甲醛的第一氧化峰电流随浓度的增加而增大,并且呈线性关系,可用于甲醛的检测。     

Improvement of the Selectivity of Amperometric Biosensors by Using a Permselective Electropolymerized Film

Abstract

Dichlorophenolindophenol (DCPIP) was electrochemically deposited onto the surface of glassy carbon and platinum electrodes to form a permselective film. Cyclic voltammetry of the DCPIP coated electrode exhibited a reversible oxidation/reduction current at +0.14 V, behavior similar to monomeric DCPIP. However, such an electrode did not mediate glucose oxidase in the presence of β-D-glucose. For operation at +0.7 V vs Ag/AgCl, the DCPIP electrodeposited film behaved like a permselective membrane and virtually eliminated oxidative interference currents resulting from 0.2 mM acetaminophen, uric acid and glutathione. For ascorbic acid, interfering current due to 0.2 mM ascorbate was decreased by 80%. Improvement of the selectivity due to ascorbic acid was achieved using an electrodeposited film prepared from a mixture of DCPIP with diaminobenzene or resorcinol.     

Electrochemical Behaviors of Ascorbic Acid and Uric Acid in Ionic Liquid

Cyclic voltammetric measurements at platinum electrode have been carried out to investigate the electrochemical oxidation of ascorbic acid and uric acid in ionic liquid, [bmim][BF₄]. It is important that a typical redox couple of ascorbic acid was obtained and it is oxidized to dehydroascorbic acid in [bmim][BF₄]. However, there is no electron-transfer for uric acid and no electrochemical oxidation carried out in the same ionic liquid. It provides a new way to eliminate the interfering between ascorbic acid and uric acid in the study of the electrochemical behaviors for them.     

Electrocatalytic oxidation and flow-injection determination of ascorbic acid at a graphite electrode modified with a polyaniline film containing electrodeposited palladium

A method for forming a composite film on the surface of a graphite electrode is proposed. Conditions for detecting the maximum catalytic current under batch and flow conditions are determined. A procedure for the electrocatalytic determination of ascorbic acid at the graphite electrode modified with a polyaniline film containing palladium particles is proposed. The catalytic effect of this electrode manifests itself by a ～300-mV decrease in the peak potential of ascorbic acid oxidation and by a multiple increase in the peak current of ascorbic acid oxidation as compared to the unmodified electrode. The linear dependence of the electrocatalytic response of the composite electrode on the concentration of ascorbic acid is observed down to 1 × 10^?8 M and 2.5 nmol of ascorbic acid under batch and flow-injection analysis conditions, respectively.     

Coulometric determination of uranium with a platinum working electrode

Experimental conditions have been established which enable uranium to be determined coulometrically by the reduction of uranium(VI) to uranium(IV) at a platinum working electrode, by controlled-potential or controlled-potential-limit techniques. The procedure has been used successfully as a subsidiary method in the routine determination of uranium in pure uranyl nitrate solutions. The platinum electrode has several important practical advantages over the well established mercury-pool electrode for the coulometric determination of uranium. The consecutive determination of iron(III) and uranium(VI), or plutonium(IV) and uranium(VI) can be carried out with the same working electrode in the same solution and the coulometric oxidation of uranium(IV) to uranium(VT) is practicable. The rate of stirring of the cell liquor is much less critical in the case of the platinum electrode. Two main problems had to be overcome before a practical procedure could be achieved; hydrogen evolution during the uranium(VI)-(IV) reduction had to be eliminated so that 100% current efficiency could be obtained for the desired reaction and electrode-surface poisoning phenomena had to be controlled so that reaction times could be kept reasonably short. It was found that selection of a hydrochloric acid base solution containing a small amount of bismuth(III) enabled hydrogen evolution to be avoided: also electrode-surface poisoning with this base solution was not particularly serious and could be maintained at a satisfactorily low level by occasionally anodizing the electrode in dilute sulphuric acid. Bismuth(III) forms a complex with chloride ions and its presence increases the hydrogen overvoltage at the working electrode: no visible deposit of bismuth metal forms on the electrode during the uranium reduction. Samples containing nitrate can be analysed provided sulphamic acid is added to this hydrochoric acid base solution.     

Surface modification of a planar electrochemical microcell

The fabrication of a three-electrode electrochemical microcell in which the working electrode is selectively modified with poly (vinylferrocene) (PVFer) is described for use as a chemical sensor. The microcell was characterized by cyclic voltammetric and differential-pulse voltammetric techniques and the behaviour of the PVFer-modified platinum electrode in contact with 0.1 M KCl is reported. The mediating properties of the PVFer film are demonstrated for this cell by using the oxidation of ascorbic acid, a process which is shown to be slow at the corresponding bare platinum microelectrode.     

Nonenzymatic glucose detection by using a three-dimensionally ordered, macroporous platinum template

A three-dimensionally ordered, macroporous, inverse-opal platinum film was synthesized electrochemically by the inverted colloidal-crystal template technique. The inverse-opal film that contains platinum nanoparticles showed improved electrocatalytic activity toward glucose oxidation with respect to the directly deposited platinum; this improvement is due to the interconnected porous structure and the greatly enhanced effective surface area. In addition, the inverse-opal Pt-film electrode responds more sensitively to glucose than to common interfering species of ascorbic acid, uric acid, and p-acetamidophenol due to their different electrochemical reaction mechanisms. Results showed that the ordered macroporous materials with enhanced selectivity and sensitivity are promising for fabrication of nonenzymatic glucose biosensors.     

(4,4′,4″,4″′-四硝基)·酞菁合钴(Ⅱ)化学修饰电极对抗坏血酸的电催化氧化

合成了一种钴的酞菁配合物,以玻碳为基体、用化学吸附法制备了它的化学修饰电极。用CV法研究了该化学修饰电极对抗坏血酸氧化的电催化作用。结果表明,该化学修饰电极对抗坏血酸的氧化有一定的电催化作用,且电催化活性的稳定性高,抗坏血酸的电催化氧化峰电流和其浓度之间有良好的线性关系。     

Atmospheric and electrochemical oxidation of ascorbic acid in anionic,nonionic and cationic surfactant systems

It is well known that the antioxidant activity of some species in homogenous solutions may not be the same as that in heterogeneous media. This environment dependence is the reason for investigating ascorbic acid antioxidant activity in surfactant solutions. In our study we have investigated the kinetics of atmospheric oxidation and electrochemical oxidation of ascorbic acid in aqueous solutions of the four surfactants: SDS, AOT (anionic), TRITON-100 (nonionic), and CTAB (cationic). For each surfactant the concentrations below and above CMC were investigated. As expected, a general trend in the atmospheric oxidation rate changes in the following manner: the micellar solution of nonionic surfactant shows a faster oxidation rate than that of the anionic surfactant, and the cationic surfactant an even higher one. The more subtle effects were observed with each surfactant concentration change. The influence of the surfactants on the electrochemical behavior of ascorbic acid was also studied. A general conclusion emerging from our investigation is that surfactants shift the ascorbic acid oxidation potential and change the peak current value. This phenomenon is due mainly to the surfactant film formed at the electrode/solution interface.     

Congo Red Immobilized on a Silica/Aniline Xerogel: Preparation and Application as an Amperometric Sensor for Ascorbic Acid

Congo red (CR) was immobilized on a silica/aniline xerogel through electrostatic interaction. The dye is strongly retained and is not easily leached from the xerogel matrix. The material containing the adsorbed dye was used to prepare a carbon paste electrode and the electrochemical properties of the hybrid material were investigated using cyclic voltammetry and amperometry. The modified electrode was used to study the electrochemical oxidation of ascorbic acid. The adsorbed dye mediates ascorbic acid oxidation at the solid electrode surface‐solution interface at an anodic potential of 0.18 V at pH 7, in a 0.5 mol L^?1 KCl solution. This novel modified carbon paste electrode shows good analytical performance for the determination of ascorbic acid in commercial Vitamin C tablets.