The mechanism of the electrogenerated chemiluminescence of luminol in aqueous alkaline solution

The mechanism of the electrogenerated chemiluminescence of luminol in aqueous alkaline solution based on the rotating ring—disc electrode system is discussed. The disc electrode is maintained at a negative potential and the ring electrode at a symmetrically changing double-step potential. Hydrogen peroxide generated at the disc electrode by the reduction of oxygen is immediately transported to the ring electrode because of electrode rotation. Hydrogen peroxide and luminol are oxidized at the ring electrode during the positive pulse of the double-step potential. These oxidation processes generate a superoxide radical and a luminol radical as intermediates. The luminol radical reacts with the superoxide radical (or oxygen) emitting light.     

Apparatus for mechanistic and analytical studies of the electrogenerated chemiluminescence of luminol

A new apparatus based on the rotating ring—disc electrode system is described. The symmetric double-step potential is connected to the ring electrode to oxidize luminol, while the disc electrode is maintained at a negative potential to reduce oxygen to hydrogen peroxide. Because of the electrode rotation, hydrogen peroxide is immediately transported to the ring electrode at which it reacts with luminol oxidation product to emit light. Preliminary electrogenerated chemiluminescence measurements indicate that the intensity of the chemiluminescence of luminol is highly dependent on the ring and disc electrode materials and that some metal ions have a catalytic or inhibitive effect on this luminescence reaction of luminol.     

Rotating Ring (Pt)–Disc (FeS2) Electrode Behavior in Hydrochloric Solutions

A rotating ring (Pt)–disc (FeS₂) electrode was used to investigate the surface oxidation process of pyrite in the hydrochloric solutions. It is reported for the first time that the oxidation intermediates of pyrite were formed on the disc electrode and then oxidized on the ring electrode. The results indicate that at a rotation rate of 20 Hz, when the disc electrode potential was in the region of 0.43 to 0.62 V and the ring electrode potential was at 1 V vs a standard calomel electrode (SCE), approximately 50% of the reacted pyrite was oxidized to ferric and sulfate ions and the other 50% was oxidized to sulfur and ferrous ions on the disc electrode. The latter was further oxidized to ferric ions on the ring electrode. As the disc electrode potential increased to 1.22 V vs SCE, more than 90% of the reacted pyrite was oxidized to ferric and sulfate ions on the disc electrode and less than 10% formed ferrous ions, which were further oxidized to ferric ions on the ring electrode.     

钴(II)与色氨酸极谱催化前波的研究

对钴(II)离子与色氨酸在H~3BO~3-NaOH(pH=9)缓冲底液中的极谱催化前波进行了形成条件、吸附性能和电极还原过程的研究。     

Cathodic electroluminescence at the terbium(III)-doped oxide-covered tantalum electrode and its feasibility for the determination of hydrogen peroxide

Anodization of the tantalum electrode with a symmetric double-step potential, (i.e., sequential positive and negative potential pulses with intermittent zero potential pulses), but not with a conventional DC potential, in an electrolyte containing traces of terbium (III) produces a terbium (III)-doped oxide film on the electrode surface. The pulsed cathodic polarization of this doped electrode in the presence of hydrogen peroxide or peroxodisulfate generates sub-bandgap electroluminescence where the oxide-bound terbium (III) is the radiative recombination center. The detailed mechanism for this terbium(III)-based sub-bandgap electroluminescence is discussed, as is the possibility of using the electroluminescence for the determination of trace hydrogen peroxide in aqueous solution.     

A Concentric Ring Electrode for a Wall‐jet Cell in a Microfluidic Device

A concentric ring array electrode that amplifies the current signal without redox cycling has been developed for highly sensitive electrochemical detection at a single potential in a microfluidic platform. Herein, the effect of ring‐electrode width on the current and current density was examined. A ring‐array electrode with widths that decrease from the inner to the outer ring was shown to exhibit the highest sensitivity. This electrode delivered a current density that was approximately 50 % higher than that of a conventionally used disc electrode. We used numerical simulations to further optimize this type of array electrode, which led to a limit of detection for catechol of 6.2 nmol/L. This ring array electrode has great potential for use in a variety of applications because it can be used to detect irreversible targets with a simple apparatus at a single potential and requires no electrode modification to achieve high sensitivity.     

Fluorophor-enhanced cathodic electroluminescence at an oxide-covered aluminum electrode

Symmetric double-step potential (i.e., positive and negative potential) pulses with intermittent zero potential pulses at the oxide-covered aluminum electrode generates anodic and cathodic electroluminescence in an aqueous environment in the presence of potassium peroxodisulfate. Organic fluorescent compounds generate changes in the cathodic electroluminescence but not in the anodic emission: intensity is greatly enhanced and the spectrum of a fluorophor-enhanced electroluminescence becomes similar to the fluorescence spectrum of the fluorophor. The mechanism of the fluorophor-enhanced peroxodisulfate-induced cathodic electroluminescence is discussed. It is demonstrated by means of salicylic acid as the model fluorophor that this electroluminescence can be exploited to determine trace organic fluorescent compounds.     

ELECTROCHEMISTRY OF NICKEL(II) TRYPTOPHAN FILM ELECTRODE AND ELECTROCATALYTIC OXIDATION OF METHANOL

A polymer film of tryptophan was obtained at a glassy carbon electrode (GC) by cyclic voltammetry. The cyclic voltammograms of the polymer film electrode(poly-Try GC) exhibited two redox waves. After incorporation of Ni(II), the electrode (poly-Ni(II) Try/GC) was greatly improved in catalytic activity. The potential 0.65 V of methanol oxidation at the poly-Ni(II)Try/GC is much more negative than the potential at the poly-Try/GC and at the bare glassy carbon (GC) electrode in 0.01 mol/L NaOH.     

Voltammetric study of the redox behaviour of the Hg(II)/Hg(I)/Hg system at a rotating metal-ring/glassy-carbon disc electrode

The reduction of Hg(II) at a glassy-carbon electrode in various electrolytes has been studied by rotating ring-disc voltammetry. Reduction proceeds directly to metallic mercury in a single 2-electron step. However, at the foot of the wave, and only during the first reduction sweep after pretreatment of the electrode surface, a small amount of Hg(I) species is detected at the ring. The appearance of an Hg(I) intermediate is most pronounced in sulphuric acid solution. The reduction of Hg(II) is found to proceed irreversibly and to be of first order. At sufficiently negative potentials the reduction is convective-diffusion controlled. Stripping voltammetric experiments indicate that the dissolution of mercury gives Hg(II) in complexing electrolytes. In non-complexing electrolytes the initially formed Hg(II) reacts with mercury atoms on the electrode surface to give Hg(I). During electrodissolution, two stripping peaks may be observed as a result of underpotential adsorption of mercury on glassy carbon. The difference in peak potential between the adsorption (mono) layer peak and the bulk mercury peak has been related to the difference in work functions of the deposit (mercury) and substrate (carbon). A rotating glassy-carbon electrode has been used for the anodic stripping determination of mercury. When an appropriate amount of a cation such as cadmium(II) or copper(II) is added to the test solution, mercury down to 2 x 10(-9)M (0.4 ng ml ) can be determined in acidified thiocyanate electrolyte with a relative standard deviation of about 22%.     

CPRM: a new method for quantitative detection of peroxide formation during oxygen reduction using the rotating ring-disc electrode technique

A new procedure to detect peroxide formation quantitatively during oxygen reduction using the rotating ring-disc electrode (RRDE) technique is described. The new procedure is called the Cyclic Potential Ring Measurement (CPRM) method. In this technique, the ring electrode is continuously cycled between 850 mV and 1600 mV versus RHE at a sweep rate of 500 . Concurrently, the disc electrode is stepped potentiostatically in the potential region of oxygen reduction. For oxygen reduction on gold, the CPRM technique indicates 100% peroxide formation in the first wave region whereas the conventional RRDE technique indicated only 20 to 30% peroxide formation. The continuous sweeping of the ring electrode in the CPRM technique regenerates continuously a fresh, active ring electrode surface that is less susceptible to interference from low levels of impurities in the solution. Consequently, the CPRM technique provides a more stable, reproducible ring surface for peroxide detection than the conventional technique.To insure that the potential sweeping of the ring does not affect its response adversely, we measured the electrode collection coefficient with a model system (Fe(CN)³⁻₆/Fe(CN)⁴⁻₆), in which low levels of solution impurities would not interfere. The collection coefficient measured using the CPRM and conventional techniques with the model system agreed within ±2.4%.     

Application of electrogenerated chemiluminescence of luminol to determination of traces of cobalt(II) in aqueous alkaline solution

A selective method for determination of traces of cobalt(II) in aqueous alkaline solution has been developed, based on the electrochemical generation of luminescence from luminol at a rotating ring—disc electrode. The detection limit is 10^-8 M, and the linear calibration range extends up to 3 × 10^-6 M; the r.s.d. for 2.0 × 10^-7 M cobalt is 6%. Of 21 metal ions, only chromium(III) and copper(II) interfere seriously; EDTA also interferes.     

Electrochemical Study of Tryptophan‐containing Peptides‐Cu(II) Complexes

This article presents rotating ring‐disc electrode investigations of (A = alanine, F = phenylalanine, G = glycine, L = leucine, W = tryptophan) W, GW, WGG, GWG, GGW, GWGG, and GGWA. In addition, the analyses of the copper complexes of the same peptides plus GF, FGG, GFG, FGG, GGFL, GGGG, AAAA, and GGGGGG have been carried out. The results suggest that an influential step in the reaction mechanism of the copper complexes of the tryptophan‐containing peptides (W‐peptides) is the alteration of the peptide structure after the one‐electron oxidation of tryptophan. This change in structure leads to a positive shift in redox potential for the Cu(III)/Cu(II) couple. The analytical implications for the electrochemical detection of W‐peptides as their copper complexes are applied for detection of W‐containing bioactive peptides. Application of the optimized detection conditions of peptides as their Cu(II) complexes are as follows: (1) If sensitivity is paramount, detect the copper complexes at a relatively high potential, around 0.7 V vs. Ag/AgCl. (2) If selectivity is paramount, use a dual electrode detector, oxidize at an upstream anode at 0.4 V, and detect at the downstream cathode at 0–0.1 V.     

Determination of traces of metals by anodic stripping voltammetry at a rotating glassy carbon ring—disc electrode: Part 1. Method and instrumentation with evaluation of some parameters

The equipment and procedure are described for the determination without preconcentration of several heavy metals based on d.c. anodic stripping voltammetry at a rotating ring—disc glassy carbon electrode with in situ mercury plating. During stripping of the metals deposited on the disc, the current from the reduction of the ions collected at the ring is measured. Some parameters (scan rate, thickness of the mercury film, electrode rotation and deposition time) influencing the ring collection peak current are examined experimentally. The results are compared with the theoretical considerations given by de Vries and van Dalen for anodic stripping voltammetry on a stationary mercury film electrode and by Bakanov et al. for a rotating mercury film electrode.     

SbO+离子的阴极还原

三价锑常用作锌粉置换法除去硫酸锌电解液中钻杂质的活化剂。在此过程中三价锑本身也被还原。置换反应本质上是一个电化学过程。因此,研究三价锑的阴极还原行为是有意义的。关于三价锑的阴极还原,Koval等研究了酒石酸盐溶液中Sb(Ⅲ)的电沉积。Tomlinson曾指出,在高电流密度下电解时,阴极上会析出锑化氢(SbH_3)。吴浩青等在研究酸性溶液中锑电极的电化学行为时,也曾指出了SbH_3的生成。本文采用旋转电极上的动电位扫描、旋转环盘电极以及交流阻抗技术研究硫酸钠溶液中SbO~+离子的阴极还原过程。     

纯锌电极上的表面增强拉曼光谱研究

通过化学刻蚀、电化学沉积和电化学氧化还原等粗糙方法,寻找合适的条件对锌电极表面进行预处理,以期获得吡啶在纯锌电极上的表面增强拉曼光谱(SERS).实验证明,电化学氧化还原处理是最佳的选择.以0.5mol/LNaClO4中性溶液作为电解质溶液,分别进行电化学氧化还原循环和电位阶跃两种处理.结果表明,将还原电位和氧化电位分别控制在-1.6和-0.7V时,利用共焦显微拉曼系统成功地得到了粗糙锌电极表面吸附吡啶的SERS信号.     

pH值对2-(2-吡啶基)咪唑荧光光谱的影响研究

合成了2-(2-吡啶基)咪唑,并通过稳态荧光光谱研究了它在溶液中的光物理行为及溶液酸碱度的影响.发现2-(2-吡啶基)咪唑化合物存在分子内光诱导电子转移反应(PET),并且这一过程强烈地依赖于溶液的pH值,但是氮原子的质子化会影响PET过程.     

Surface-enhanced Raman scattering at the silver electrode/ionic liquid (BMIPF6) interface

This is the first report of in situ SER spectra of chemical species adsorbed on a Ag/room temperature ionic liquid (RTIL) interface. We have investigated the dependence of the SERS intensity of the RTIL derived from 1-n-butyl-3-methylimidazolium hexafluorophosfate (BMIPF6) adsorbed on a silver electrode. It has been shown that the BMI+ adsorbs on the silver electrode for potentials more negative than -0.4 V vs a Pt quasireference electrode (PQRE). In the -0.4 to -1.0 V potential range the SER spectra are similar to the Raman spectrum of the RTIL BMIPF6. At potentials more negative than -1.0 V some imidazolium ring vibrational modes and N-CH3 vibrations are enhanced, suggesting that the imidazolium ring is parallel to the surface and for potentials <-2.8 V the BMI+ is reduced to the BMI carbene. The potential dependence of the SERS intensities of Py adsorbed on a silver electrode in BMIPF6 has also been investigated. The results have shown that at potentials less negative than -0.8 V (vs PQRE) Py adsorbs at an end-on configuration forming an Ag-N bond. In the -0.9 to -1.4 V potential range Py molecules lie flat on the electrode surface and at potentials <-1.4 V Py is replaced by the BMI+. The electrochemical and SERS results have shown that Py has the effect of changing the oxidation of silver in that medium as well as the reduction of BMI+ to the BMI carbene. In the presence of Py the BMI+ reduction is observed at potentials near -2.4 V. The Ag electrode has presented SERS activity from 0.0 to -3.0 V.     

Development of a versatile rotating ring-disc electrode for in situ pH measurements

There are some electrocatalytic reactions in which the key parameter explaining their behavior is a local change in pH. Therefore, it is of utter importance to develop an electrode that could quantify this parameter in situ, but also be customizable to be used in different systems. The purpose of this work is to build a versatile rotating ring/disc electrode (RRDE) with IrO_x deposited on a glass tube as a ring and any kind of material as disc. As the IrO_x is sensitive to pH variation, the reactions promoted on the disc can trigger proportional pH shifts on the ring. In such assembly, the IrO_x ring presents a fast response time even during the pH transients due to the small thickness of the ring (approximately 10 μm), which enables the detection of interfacial pH changes. The ring electrode was tested toward the interfacial pH shift observed during the electrolytic reduction of water on the disc and also characterized by acid–base titration to determine the response time. As the main conclusions, fast response and durable RRDE were obtained, and this assembly could be used to revisit many electrocatalytic reactions in order to test the importance of local pH on the process.     

Electrocatalytic Oxidation of Methanol on a Nickel‐Porphyrin IX Complex Modified Glassy Carbon Electrode in Alkaline Medium

Electrocatalytic oxidation of methanol on a glassy carbon disc electrode modified with Ni(II)‐hematoporphyrin IX, complex and conditioned by potential recycling in a limited range (between 100 and 600 mV vs. SCE) in 0.10 M NaOH solution, abbreviated as NiOHPME(A), was studied by cyclic voltammetry in alkaline medium. The results were compared with those obtained for a NiO modified glassy carbon electrode, NiOME, prepared in similar conditions. The findings show that the NiOHP film at NiOHPME(A) behaves as an efficient electrocatalyst for the oxidation of methanol in alkaline medium via Ni(III) species with the cross‐exchange reaction occurring throughout the layer at a low concentration of methanol and for a thin film of modifier. A plausible mechanism was proposed for catalytic oxidation of methanol at NiOHP modified electrode. Moreover, the effects of various parameters such as the scan rate, methanol concentration, thickness of NiOHP film and the real surface area of modified electrode on the oxidation of methanol were investigated. Finally, it has been shown that the NiOHPME(A) has a long‐term stability toward the oxidation of methanol.     

Exploiting flow injection and sequential injection anodic stripping voltammetric systems for simultaneous determination of some metals

Flow injection (FI) and sequential injection (SI) systems with anodic stripping voltammetric detection have been exploited for simultaneous determination of some metals. A pre-plated mercury film on a glassy carbon disc electrode was used as a working electrode in both systems. The same film can be repeatedly applied for at least 50 analysis cycles, thus reducing the mercury consumption and waste. A single line FI voltammetric system using an acetate buffer as a carrier and an electrolyte solution was employed. An injected standard/sample zone was mixed with the buffer in a mixing coil before entering a flow cell. Metal ions were deposited on the working electrode by applying a potential of −1.1 V vs Ag/AgCl reference electrode. The stripping was performed by anodically scanning potential of working electrode to +0.25 V, resulting a voltammogram. Effects of acetate buffer concentration, flow rate and sample volume were investigated. Under the selected condition, detection limits of 1 μg l⁻¹ for Cd(II), 18 μg l⁻¹ for Cu(II), 2 μg l⁻¹ for Pb(II) and 17 μg l⁻¹ for Zn(II) with precisions of 2–5% (n=11) were obtained. The SI voltammetric system was similar to the FI system and using an acetate buffer as a carrier solution. The SI system was operated by a PC via in-house written software and employing an autotitrator as a syringe pump. Standard/sample was aspirated and the zone was then sent to a flow cell for measurement. Detection limits for Cd(II), Cu(II), Pb(II) and Zn(II) were 6, 3, 10 and 470 μg l⁻¹, respectively. Applications to water samples were demonstrated. A homemade UV-digester was used for removing organic matters in the wastewater samples prior to analysis by the proposed voltammetric systems.