ELECTROCHEMICAL CATALYSIS AT AN ULTRAMICROELECTRODE MODIFIED WITH REDOX SPECIES

General equations of the electrocatalytic reaction at an ultramicroelectrode modified with redox species have been described according to the Andrieux Saveant model. The electrocatalytic kinetic process has been discussed for the whole set of cases, ie (R), (R + S), (SR) (SR + E), (E), (R + E), (ER), (S), (ER + S) and (S + E) limiting situations. The effect of gamma on the catalytic steady state current shows that the higher the value of gamma, the lower the catalytic current. The kinetic process shifts rapidly from R to E with increasing values of gamma. It is favorable for catalysis only when gamma is very low. Therefore, the redox species modified ultramicroelectrode with thin film is utilized for electrocatalysis, and the larger the radius of ultramicroelectrode, the higher the catalytic efficiency.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

AMPEROMETRIC DETECTION OF CATECHOLAMINES WITH LIQUID-CHROMATOGRAPHY AT A NOVELLY CONSTRUCTED PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.

FLOW-INJECTION AMPEROMETRIC DETECTION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

A Prussian Blue-modified glassy carbon electrode prepared by simple adsorption exhibited excellent electrocatalytic activity in the oxidation of hydrazine in acidic media. A film of the perfluorosulphonic acid polymer Nafion coated on top of the Prussian Blue-modified glassy carbon electrode can improve the mechanical stability of the Prussian Blue layer in the flow stream. Hydrazine was detected by flow-injection analysis at the modified electrode with high sensitivity. The limit of detection was 0.6 ng.

AMPEROMETRIC FLOW-INJECTION ANALYSIS OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT COBALT TETRAPHENYLPORPHYRIN MODIFIED ELECTRODE WITH HEAT-TREATMENT

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750-degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH3OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4-mu-g. The method is very sensitive and selective.

ELECTROCHEMICAL STUDY OF ISOPOLYOXOMETALLATES AND HETEROPOLYOXOMETALLATES FILM MODIFIED MICROELECTRODES .1. PRETREATMENT AND MODIFICATION OF THE MO80-26(4-) MODIFIED CARBON-FIBER MICROELECTRODE

In this paper the preparation of isopoly- and heteropolyoxometallates (IPA and HPA) thin film modified carbon fiber (CF) microelectrodes and the factor that influences the modification of IPA and HPA films are described. IPA and HPA film modified CF microelectrodes can all be prepared by cyclic potential scan and simple dip coating. The modified electrodes prepared are very stable and reversible in acidic solution with monolayer characteristics. The electrochemical pretreatment of CF microelectrodes plays an important role in the modification of IPA and HPA film. The absorption of IPA and HPA film on electrode surfaces has been discussed on the basis of surface conditions of the CF microelectrode and the structure of IPA and HPA.

LIQUID-CHROMATOGRAPHY WITH ELECTROCATALYTIC DETECTION OF CYSTEINE, N-ACETYLCYSTEINE AND GLUTATHIONE BY A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

Chemically modified electrodes prepared by adsorbing prussian blue on a glassy carbon electrode are shown to catalyse the electro-oxidation of cysteine, N-acetylcysteine and glutathione in acidic media. The catalytic response is evaluated with respect to the potential scan rate, the solution pH, the concentration dependence, and other variables. Covering the electrode with Nafion(R) film improved the stability and reproducibility in liquid chromatography with electrochemical detection to the extent that repetitive sample injections produced relative standard deviations of less than 5% over several hours of operation. The limit of detection was 4 pmol for cysteine, 33 pmol for glutathione and 61 pmol for N-acetylcysteine.

铁氰化钴修饰电极的制备、表征及电催化性能的研究

多核过渡金属铁氰化物修饰电极的研究在电催化、电色显示器件、能量存储、离子识别等方面具有重要的意义。本文采用了电化学的循环伏安法（CV）、旋转圆盘电极技术（RDE）、傅立叶变换红外光谱法（FTIR）和扫描电子显微镜技术（SEM），系统研究了一类铁氰化物—铁氰化钴修饰玻碳（CoHCF／GC）电极的制备方法及其对神经递质多巴胺（DA）的电催化作用以及修饰溶液中一种阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）的加入对所制备的CoHCF／GC电极的电化学性能和电催化性能的影响。主要内容和结论如下：1．改进了CoHCF／GC电极的制备方法。新方法具有简单易行、不受修饰物浓度干扰、修饰时间短、修饰量易于控制等优点，且制备的CoHCF粒径小、结构明确、电化学性能稳定。2．研究了CoHCF／GC电极对DA氧化的电催化性能。采用RDE测定了CoHCF／GC电极对DA的电催化氧化的动力学参数。结果表明用新方法制备的修饰电极对DA氧化有更好的电催化性能。3．研究了在修饰溶液中加入临界浓度的CTAB对所制备的CoHCF／GC电极的影响。CV的研究结果表明，CTAB的加入，基本不影响CoHCF／GC的氧化还原峰峰电位，却使其氧化还原峰峰电流明显增大，且使所制得CoHCF／GC电极对DA氧化表现出不同的电催化行为。FTIR研究表明，CTAB不吸附在电极表面，不改变COHCF膜的化学组成和结构。SEM研究结果表明，CTAB的加入使所制备的CoHCF膜长得更快，更厚，使CoHCF粒子长得更大。因此，可得出结论为CoHCF粒子的大小是影响其对DA不同的电催化行为的主要因素。4．用RDE技术测定了有、无CTAB情况下制备的CoHCF／GC电极对DA的电催化反应的动力学参数。结果表明，有CTAB时制备的CoHCF／GC电极对DA的表观动力学常数kΓ比没有时的要大。

聚吡咯膜个饰电极的研究

1）本文首次制备了掺杂六氰亚铁铜胶体微粒的聚吡咯膜修饰电极，并用XPS，SEM等手段对其进行了表征。研究了此修饰电极的电化学行为，离子选择性行为及光谱电化学行业；2）利用聚吡咯膜修饰电极成地实现了神经递质三磷酸腺苷（ATP）的电化学控制释放；3）利用计时库仑法和交流阻抗法对掺杂电活性物质的聚吡咯膜修饰电极膜内的电子传输机理进行了详细的研究；4）研究了掺杂靛红的聚吡 咯膜的电色效应现象。合成了磺化二茂铁，并成功地将其掺入PPy膜中，制成功能化的PPy膜修饰电极。

Determination of concentrated hydrogen peroxide at single-walled carbon nanohorn paste electrode

Single-walled carbon nanohorn (SWCNH) paste electrode was used for amperometric determination of concentrated hydrogen peroxide, and was compared with other carbon electrodes. The calibration plots are linear from 0.5 to 100 mM at activated SWCNH paste electrode and edge plane graphite (EPG) electrode. In contrast, the calibration plots are linear only at concentrations lower than 45 mM at graphite paste electrode, multi-walled carbon nanotube paste electrode, and glassy carbon electrode.

Amperometric glucose biosensor based on single-walled carbon nanohorns

The biosensing application of single-walled carbon nanohorns (SWCNHs) was demonstrated through fabrication of an amperometric glucose biosensor. The biosensor was constructed by encapsulating glucose oxidase in the Nafion-SWCNHs composite film. The cyclic voltammograms for glucose oxidase immobilized on the composite film displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of -0.453V. The biosensor had good electrocatalytic activity toward oxidation of glucose.

Direct electron transfer of horseradish peroxidase and its electrocatalysis based on carbon nanotube/thionine/gold composites

Horseradish peroxidase (HRP) was incorporated into multiwalled carbon nanotube/thionine/Au (MTAu) composite film by electrostatic interactions between positively charged HRP and negatively charged MTAu composite. The results of electrochemical impedance spectroscopy (EIS) confirmed adsorption of HRP on the surface of MTAu modified GC electrode.

Preparation of Prussian blue@Pt nanoparticles/carbon nanotubes composite material for efficient determination of H2O2

In this study, the fabrication of an efficient amperometric hydrogen peroxide sensor with favorable properties is presented. Prussian blue (PB) was catalytically synthesized by Pt nanoparticles (Pt-nano) from ferric ferricyanide aqueous solution to form PB@Pt-nano hybrid, and it was confirmed by transmission electron microscope (TEM) and optical spectra. The electrochemical behavior of PB@Pt-nano was highly improved through its integration with poly(diallyldimethylammonium chloride) modified carbon nanotubes (PCNTs).

Single-walled carbon nanohorn as new solid-phase extraction adsorbent for determination of 4-nitrophenol in water sample

Single-walled carbon nanohorn (SWCNH) was developed as new adsorbent for solid-phase extraction using 4-nitrophenol as representative. The unique exoteric structures and high surface area of SWCNH allow extracting a large amount of 4-nitrophenol over a short time. Highly sensitive determination of 4-nitrophenol was achieved by linear sweep voltammetry after only 120 s extraction. The calibration plot for 4-nitrophenol determination is linear in the range of 5.0 x 10(-8) M-1.0 x 10(-5) M under optimum conditions. The detection limit is 1.1 x 10(-8) M. The proposed method was successfully employed to determine 4-nitrophenol in lake water samples, and the recoveries of the spiked 4-nitrophenol were excellent (92-106%).

Direct electrochemistry of glucose oxidase and biosensing for glucose based on carbon nanotubes@SnO2-Au composite

Multiwalled carbon nanotubes@SnO2-Au (MWCNTs@SnO2-Au) composite was synthesized by a chemical route. The structure and composition of the MWCNTs@SnO2-Au composite were confirmed by means of transmission electron microscopy, X-ray photoelectron and Raman spectroscopy. Due to the good electrocatalytic property of MWCNTs@SnO2-Au composite, a glucose biosensor was constructed by absorbing glucose oxidase (GOD) on the hybrid material. A direct electron transfer process is observed at the MWCNTs@SnO2-Au/GOD-modified glassy carbon electrode. The glucose biosensor has a linear range from 4.0 to 24.0 mM, which is suitable for glucose determination by real samples. It should be worthwhile noting that, from 4.0 to 12.0 mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations in human blood. Meanwhile, the resulting biosensor can also prevent the effects of interfering species.