The sers of pyridine on an electrochemically plated silver electrode

Surface-enhanced Raman scattering (SERS) of pyridine adsorbed on silver electrodes prepared by an electrochemical plating method was studied. This EP A     

Mn3+/Mn2+氧化还原体系的旋转圆盘电极法性能

氧化还原液流电池的独特性能受到关注[1～4]。本文综合运用循环伏安法,旋转圆盘电极法研究锰离子浓度较高(0 25～0 35mol·L-1、转速范围较宽(400～4200rpm)、同时考虑过电位的条件下Mn(Ⅲ)/Mn(Ⅱ)电对在RDE铂盘电极上的电极过程动力学并确定有关的动力学参数,了解其影响因素,为该电对作为氧化还原液流电池正极活性材料提供动力学依据。1　实验部分铂电极使用前在铬酸洗液中浸10min,水冲洗干净,蒸馏水淋洗,然后在6 3mol·L-1H2SO4中超声清洗10min,再用CHI660电化学工作站(美国CH仪器公司)控制,以0 05V/s的扫速在-1 0～1 2V之间扫…     

Multi-electron oxidation of formaldehyde on a platinum electrode

The time evolution of a self-sustained potential oscillation under constant current oxidation of formaldehyde was observed on the rotating ring disk electrode assemble. Under the condition when the potential was controlled, the laser deflection voltammogram as well as the conventional cyclic voltammogram were measured. The mechanism of the multi-electron oxidationof formaldhyde on a platinum electode is discussed.     

A membrane electrode for nitrate and other univalent anions

A membrane electrode has been developed which is responsive to nitrate and other univalent anions but non-responsive to sulphate and other multivalent anions and to cations other than hydrogen. The membrane is prepared by polymerizing a mixture of phenol, formaldehyde, ammonia and nickel nitrate directly to a film for mounting in the usual cell-with-membrane assembly. Response to hydrogen ion is 0.30 mV per pH unit, to nitrate 0.60 mV per pNO(3) (activity) unit. Based on chemical composition and behaviour, physical properties, and electrical response, a structure and mechanism for exchange with hydrogen ion and nitrate ion and for internal electrical conduction has been postulated. Applications have been made to the determination of nitrate and to the detection of end-points.     

Electrooxidation and adsorption of oligoelthylene glycols on platinized platinum electrode

The trends in adsorption and oxidation of oligoethylene glycols (OEG), namely, di-, tri-, and tetraethylene glycol, on a Pt/Pt electrode are studied. Using a combination of methods of open-circuit potential shifts at the adsorption of organic species and anodic voltammetric curves, it is established that the OEG adsorption on a Pt/Pt electrode is accompanied by hydrogenation, dehydrogenation, and partial destruction of molecules and also that the amount and composition of accumulated adsorbate depend on the initial adsorption potential and the polymer structure. The OEG oxidation on a platinum electrode is considerably hindered as compared with ethylene glycol. The reaction rate decreases with an increase in the OEG molecular mass and is largely limited by the adsorption of molecules on the electrode surface, which is evidenced by the weak dependence of the rate on the potential in the double layer region.     

Immobilization of enzyme to platinum electrode and its use as enzyme electrode

A glucose electrode was fabricated by immobilizing glucose oxidase covalently onto a platinized platinum electrode. The sensor showed rapid response with response time of 2—4 s, and also the linear response to the glucose concentration, ranging from 2 x 10^-3 to 5 mM. The sensitivity was found to be correlated with the surface area of a base electrode used.     

Potential-assisted assembly of functionalised platinum nanoparticles on electrode surfaces

A method for assembling Pt nanoparticles (5 nm diameter) on indium tin oxide (ITO) and highly oriented pyrolytic graphite (HOPG) electrodes, via the potential-assisted deposition of pre-formed perthiolated-β-cyclodextrin-capped Pt nanoparticles is described. Cyclic voltammetry allowed control over the surface coverage of monodisperse Pt nanoparticles in a simple fashion, as evidenced by the voltammetric response and atomic force microscopy of the resulting electrode surface. The Pt nanoparticle arrays formed in this way were electrocatalytically active towards proton reduction-hydrogen evolution. The methodology described thus opens up a new approach for the deposition of metal nanoparticles with controlled surface density for the investigation of electrocatalytic processes.     

Determination of nitrate and nitrite in mixtures with a nitrate ion electrode

A rapid method for the determination of nitrate and nitrite ions is described. The potential of a mixture of nitrate and nitrite was measured with a nitrate ion selective electrode. The nitrite in the mixture is then oxidized to nitrate with permanganate in acid solution, and the potential of the oxidized solution is also measured with the electrode. The fundamental equations for the response of the nitrate ion electrode to nitrate ion in the presence of interfering ions were used, and a new equation was developed for calculating the original nitrate concentration of the mixture. The absolute errors for solutions of known concentrations (2.5–100 p.p.m. each) were 1.8 p.p.m. nitrate and 2 p.p.m. nitrite. When the results are calculated by computer, five determinations can be performed in 30 min. The method was applied to the determination of the oxides of nitrogen in cigarette smoke as nitrite and nitrate after dissolution in basic solution.     

The adsorption of carbon monoxide on a platinum electrode

The adsorption of CO from 0.5 M H₂SO₄ solution on platinum has been studied using CO labelled with C-14. The adsorption of CO on Pt occurs in the potential range of hydrogen adsorption as well as in the double layer region. In the whole potential range the rate of adsorption follows first order kinetics. From the surface concentrations and charges for oxidation of adsorbed species it follows that the product of chemisorption consists at least of two kinds of species. One of them is the COOH radical probably formed by the reaction of CO with water.     

Anodic oxidation of cyanide and cyanate ions on a platinum electrode

The oxidation processes of cyanide and cyanate ions on a Pt electrode in aqueous and methanol solutions were studied by infrared spectroscopy. In aqueous solution, the cyanide ion was oxidized to cyanate and successively to carbon dioxide. The reaction proceeded on an oxidized platinum surface. In methanol solution, HNCO is the main product during anodization.     

A selective electrolytic sensor for nitrite based on a modified platinum electrode

The electrolytic sensor described is based on the oxidation of nitrite at a platinum electrode modified with chemisorbed iodine and coated with a thin layer of quaternized poly(4-vinylpyridine), qPVP. The sealed sensor uses an anion-exchange membrane to separate Donnan transport of nitrite across the membrane and controlled potential electrolysis at the Pt/qPVP indicator electrode. The sensor has a linear response to nitrate concentration in aqueous samples over the range 4 × 10^?6?2 × 10^?3 M nitrite. The detection limit is 2 × 10^?6 M nitrite. The sensor is free of interference by nitrate, dissolved oxygen, cations, and many neutral species. Anions that are electroactive at 0.7 V vs. Ag/ AgCl would interfere, but they are uncommon in most samples. Initial tests with lake water samples suggest that this sensor is unaffected by this matrix. The system was also evaluated for monitoring nitrite levels in spiked meat extracts.     

Photoinduced surface dynamics of CO adsorbed on a platinum electrode

The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation.     

Electrochemical reduction of decafluorobenzil in DMF on a platinum electrode

The mechanism of electrochemical reduction of decafluorobenzil on a platinum electrode in DMF was investigated by cyclic voltammetry. The first reduction peak corresponded to a reversible single-electron transfer leading to the formation of a relatively stable anion-radical whose ESR spectrum was registered and characterized. The second peak corresponded to the reduction of the anion-radical into an unstable dianion that quickly reacted with initial decafluorobenzil, and the arising species (or its transformation product) at the given potential underwent further reduction. The effect of fluorine on the potentials and on the mechanism of the electrochemical reduction of decafluorobenzil was considered.     

Electrochemical oxidation of the nickel-EDTA complex on a platinum electrode

The electrochemical formation of a Ni(III)-EDTA (EDTA=ethylenediaminetetra-acetate) precipitate on a Pt electrode is observed. This precipitate can be reduced without dissolution. The electrochemical properties of this precipitate are analysed and compared with those of other tervalent nickel complexes.     

Adsorption of polyethylene glycol on platinum electrode from acidic solutions

The effect of the molecular mass of polyethylene glycol (PEG) on its adsorption on platinized platinum from aqueous solutions of 0.5 M H₂SO₄ and 1 M HCl is studied using the methods of open-circuit potential shifts and voltammetry. In sulfuric acid solutions, the PEG adsorption is accompanied by dehydrogenation and hydrogenation processes, which probably involve the terminal groups of polymers. For PEG with the molecular mass of 600–40000, the established stationary surface states turn out to be close to one another. Anions Cl^? inhibit the PEG adsorption and electrooxidation. The adsorption behavior of PEG samples studied substantially differs from that of ethylene glycol under comparable conditions.     

Adsorption of water on a platinum electrode from dimethylsulphoxide solution

Adsorption of water from DMSO solution on platinum was studied by the use of the direct tritium radioelectrochemical method. It was found that adsorption occurs in the second ad-layer of the Pt-DMSO interface with the maximum surface concentration 1.1×10¹⁵ mol cm^?2. This value was attributed to the monolayer of the adsorbate. Formally, Temkin conditions were found. No potential dependence of HTO adsorption was observed. Some remarks on the double-layer structure of the Pt electrode in DMSO are included.The potential dependence of DMSO adsorption previously determined with the ³⁵S compound has now been confirmed by using T-labelled DMSO. This is considered as evidence that no H-T isotope exchange between chemisorbed DMSO and water from the solution phase occurs.