Electrochemical study of chemically modified and screen-printed graphite electrodes with

The preparation and electrochemical characterization of graphite electrodes modified with hexadecylpyridinium-bis(chlorilato)-antimonyl(V), [SbVO(CHL)2]Hex, (CMEs) as well as their behavior as electrocatalysts toward the oxidation of sulfide are described. The self-exchange rate constant ko of immobilized [SbVO(CHL)2]Hex and the effect of the surface coverage were evaluated. [SbVO(CHL)2]Hex is a new compound. Synthesis protocol and some identification studies are given. The fabrication of screen-printed electrodes (SPEs) with a mixture of 5% (w/ w) [SbVO(CHL)2]Hex/graphite powder in 1.5% (w/v) ethyl cellulose in 2-butoxyethyl acetate is also described. SPEs, poised at +0.08 mV versus Ag/AgCl, at pH 6.5 were utilized for the determination of sulfide in simulated wastewater samples. Interference of various compounds was also tested. The proposed method correlates well with a colorimetric method. Calibration graphs were linear over the range 0.01-0.7 mM sodium sulfide and the CV was 2.8% (n = 8) for 0.1 mM sodium sulfide. Recovery ranged from 94 to 102%. Both [SbVO(CHL)2]Hex CMEs and SPE showed very good storage stability. [SbVO(CHL)2]Hex CMEs showed poor working stability in contrast to printed electrodes, which operated with no remarkable loss of their initial activity for more than 100 runs.     

Electrochemical and XPS characterization of composite modified electrodes obtained by nickel deposition on noble metals

A chemically modified electrode composed of nickel oxyhydroxide film deposited on noble metals (i.e., gold or platinum) was characterized in an alkaline medium by cyclic voltammetry and XPS (X-ray photoelectron spectroscopy) techniques. The nickel was deposited on the gold substrate in an alkaline medium by various strategies: cycling the potential between -0.1 and 0.65 V vs SCE, in potentiostatic conditions at potentials comprised between 0.0 and 0.55 V and by simple immersion of the electrode in non-deaerated 0.2 M NaOH solutions containing 3 mM K2Ni(CN)4. The effects of several experimental parameters such as applied potentials, pH, tetracyanonickelate concentration, electrode substrate, etc., on the nickel film formation and growth were evaluated. The electroactivity of the resulting composite gold-nickel electrode was investigated in an alkaline medium toward the oxidation of carbohydrates using arabinose as a model compound.     

Electrochemical behavior of ascorbate oxidase immobilized on graphite electrode modified with Au-nanoparticles

Direct electrochemistry of ascorbate oxidase was observed when immobilized on graphite modified with nano-sized gold structures. Au-structures were electrodeposited onto the graphite surface by means of cyclic voltammetry, then the enzyme was chemisorbed onto their surface. The electron transfer between the enzyme active center and the modified electrode surface was probed by square wave voltammetry (SWV) and cyclic voltammetry (CV). The dependence of the current maxima on the scan rate was found linear, suggesting that the redox process is controlled by surface chemistry. Bioelectrocatalytic oxidation of the enzyme substrate l-ascorbic acid was explored by constant potential amperometry over the potential range from 200 to 350 mV (vs. Ag/AgCl, 3 M KCl) at the рНs 5.6 and 7.0. At a potential as low as 200 mV, pH 7.0 and temperature 25 °C following operational parameters were determined for the enzyme electrode: a sensitivity: 1.54 μA mM⁻¹ mm⁻² (r² = 0.99₅), linear dynamic range up to 3.3 mМ, detection limit of 1.5 μМ, response time up to 20 s.     

Direct DNA hybridization at disposable graphite electrodes modified with carbon nanotubes

The performance of glassy carbon (GCE) and graphite pencil electrodes (PGE) modified with multiwalled carbon nanotubes (CNTs) are compared, based on the direct electrochemical detection of nucleic acids. This is accomplished by monitoring the differential pulse voltammetry changes of the guanine signal. CNT-modified PGE compares favorably to that of the commonly used CNT-modified GCE owing to the intrinsic improved performance of the supporting PGE. The better intrinsic characteristics of the PGE are related to its composite structure and higher level of porosity compared to GCE. The performance characteristics of the direct DNA hybridization on the disposable CNT-modified PGE are studied in terms of optimum analytical conditions such as probe concentration, target concentration, hybridization time, and selectivity. The new DNA biosensor described here has shown some important advantages such being inexpensive, sensitive, selective, and able to generate reproducible results using a simple and direct electrochemical protocol.     

Voltammetric separation of dopamine and ascorbic acid with graphite electrodes modified with ultrafine TiO2

In this paper, a new method was introduced to separate dopamine and ascorbic acid simultaneously. When a graphite electrode was modified with nanosized TiO₂ powder, it exerted little influence on the redox behavior of dopamine, but led to the anodic potential of ascorbic acid to move negatively which enlarged the anodic separation potential between dopamine and ascorbic acid to some extent. Better separation could be achieved with bare C and TiO₂ modified electrode at higher scan rate. The catalytical ability of nanosized metal oxide on the voltammetric behavior of dopamine and ascorbic acid was discussed as well.     

Gas permeability of graphite foil modified with iron,cobalt, and nickel oxides

Graphite foils containing iron(III), cobalt(II), and nickel(II) oxides have been prepared via the impregnation of oxidized graphite in aqueous FeCl₃, Co(NO₃)₂, and Ni(NO₃)₂ solutions, followed by exfoliation via thermal shock and pressing of the resultant exfoliated graphite. The materials thus prepared have been characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. We have studied the gas transport properties of the modified graphite foil samples and observed a considerable increase in the nitrogen and hydrogen permeabilities of the metal oxide-modified graphite foils relative to the unmodified graphite foil. The thermal properties of the samples have been studied by thermogravimetry and differential scanning calorimetry. The results demonstrate that their oxidation onset temperature reaches 570°C.     

Adsorption of hydrogen sulfide on graphite derived materials modified by incorporation of nitrogen

Adsorbents for hydrogen sulfide were prepared by heat treatment at 950 °C of spent graphite oxide based materials previously used as ammonia removal media. The materials were characterized using adsorption of nitrogen, potentiometric titration, thermal analysis, FTIR and XRD. The dynamic adsorption experiments showed an enhanced adsorption capacity owing to the presence of basic nitrogen functionalities. Although on the surface of adsorbents hydrogen sulfide was mainly oxidized to elemental sulfur small amount of SO₂ was also formed. The removal capacity was found to depend on the dispersion of nitrogen containing species, which is governed by the porosity and structure of the adsorbents. The amount of nitrogen incorporated depends on the amount of ammonia on the surface and on the surface reactivity. The latter is determined by the amount of oxygen containing groups and the level of structural heterogeneity.     

Basal plane pyrolytic graphite modified electrodes: comparison of carbon nanotubes and graphite powder as electrocatalysts

The oxidations of NADH, epinephrine, and norepinephrine are studied using carbon nanotube and graphite powder-modified basal plane pyrolytic graphite electrodes. Immobilization is achieved in two ways: first, via abrasive attachment of multiwall carbon nanotubes or graphite powder by gently rubbing the electrode surface on a fine quality paper supporting the desired material; second, via "film" modification from dispersing either graphite powder or nanotubes in acetonitrile and pipeting a small volume onto the electrode surface and allowing the solvent to volatilize. While electrocatalytic behavior of both types of nanotube-modified electrodes is shown, with enhanced currents and reduced peak-to-peak separations in the voltammetry in comparison with naked basal plane pyrolytic graphite, similar catalytic behavior is also seen at the graphite powder-modified electrodes. Caution is, therefore, suggested in assigning unique catalytic properties to carbon nanotubes.     

Electrochemical performance of modified synthetic graphite for lithium ion batteries

The carbon-coated composite has been manufactured and investigated as the negative electrode for Li-ion batteries. The carbon-coated composite powders are prepared by a simple mixing of two types of synthetic graphite particles (SFG6 and SFG44) with polyvinylchloride powders and heating to a temperature between 800 and 1100°C under an argon gas flow.As a result of the carbon-coating treatment, the flake particles of the original graphites changed into a bulky shape of carbon-coated composite with a largely increased particle size due to aggregation through the treatment. It is shown that carbon-coated composite electrodes for the two types of graphite have much lower irreversible loss than the original graphites and coulombic efficiency of 91% in the first cycle in a PC-based electrolyte. The carbon coating treatment improves the cycling performance. Despite their coarse morphology due to aggregation, carbon-coated composite electrodes show the enhanced high rate capabilities.     

Electrochemical monitoring of proton transfer across liquid/liquid interfaces on the surface of graphite electrodes

Equilibrium partitioning of HClO4 between aqueous solutions and benzonitrile (BN) or nitrobenzene (NB) was measured and used to evaluate the pKa of the acid in the two organic solvents. The potential drop across the BN/ H2O interface was evaluated from the known potential drop across the NB/H2O interface and the voltammetrically measured formal potential of a ferrocenium/ferrocene redox couple confined within thin layers of the two organic solvents. The voltammetric reduction of tetrachloro-1, 4-benzoquinone in thin layers of BN was used to monitor changes in the concentration of protons in the layer during proton-consuming faradaic reactions. The rate of proton transfer from the aqueous to the nonaqueous phase across the BN/H2O interface was shown to be adequate to sustain proton-consuming reactions at the electrode/BN interface.     

Electrochemical characterization of binderless, recompressed exfoliated graphite electrodes: electron-transfer kinetics and diffusion characteristics

Exfoliated graphite (EG) is prepared by the thermal exfoliation of graphite intercalation compounds at different temperatures. Surface and bulk physicochemical properties of EG are followed by spectroscopic and analytical methods and are observed to be a function of exfoliation temperature. EG particles can be recompressed without any binder and used as surface-renewable electrodes. Surface preparation is accomplished by either polishing or roughening the electrode surface using emery sheets. Effects of exfoliation temperature and the surface preparation on the electron-transfer kinetics and on the diffusion characteristics have been followed by electrochemical methods using several benchmark redox systems. It is found that the electron-transfer kinetics and the diffusion of K(4)[Fe(CN)(6)] are affected by the nature of the EG surface while that of iron(II)(1,10-phenanthroline)(3) and cobalt(II)(1,10-phenanthroline)(3) are not affected by the surface preparation. The redox systems are classified into different groups according to their kinetic sensitivity. Diffusion of electroactive species toward the EG electrodes is found to nonlinear. Current-time plots suggest that the recompressed EG electrodes can be modeled as fractals.     

Electrochemical and corrosion studies of copper and nickel in mixed N-methylformamide-water solutions

An electrochemical and corrosion study of copper and nickel in various mol percent (m/o) compositions of N-methylformamide and water has been carried out potentiostatically at 35 ±1 °C. Frequent active-passive transitions are observed and the critical current density for passivity is found to be dependent on the content of N-methylformamide in the solution. Nickel is found to be quite resistant to these solutions.     

Electrochemical characterization of electrodes with submicrometer dimensions

The construction and electrochemical characterization of electrodes with submicrometer dimensions (2 nm < r(app) < 1000 nm) is reported. Electrodes are prepared by insulating etched Pt wires with electrophoretic paint, as recently reported by Slevin et al. (Electrochem. Commun. 1999, 1, 282). The voltammetric behavior of these electrodes was evaluated using nine different redox systems; well-defined and stable diffusion-limited responses were obtained in all but two cases. The behavior of these electrodes was investigated in aqueous ferrocenylmethyltrimethylammonium (FcTMA+) solutions in the presence and absence of excess supporting electrolyte to determine the influence of diffusion and migration on molecular transport in the nanometer spatial regime. Our findings indicate that the voltammetric behavior of these electrodes can be described using classical transport theory for r(app) > 10 nm.     

纳米级氢氧化镍和钴对镍电极性能的影响

通过充放电曲线和交流阻抗谱的测定探讨了纳米级氢氧化镍和氢氧化镍表面包复CoOOH以及镍箔上电镀钴层对氢氧化镍粉末压制的镍电极性能的影响。结果表明．纳米级氢氧化镍有较快的活化能力，CoOOH包Ni(OH)2则有较高的放电容量，而比例适当的纳米复合镍电极才有更好的电化学性能。氢氧化镍表面包复CoOOH可改善镍电极的充放电性能；镍箔上镀钴可大大降低电极过程的电荷转移电阻；钴含量大于3％后．虽然活化速度有所下降，但是大电流充放电时，镍电极活性物的利用率更高，放电容量更大。纳米级Ni(OH)2含量大于30%后，镍电极的活化速度不仅未能加快，反而略有减慢，而且容量也降低。     

Electrochemical studies of nano-structured diamond thin-film electrodes grown by microwave plasma CVD

In this paper, we report the investigation of the electrochemical properties of nano-structured diamond thin-film electrodes on porous silicon (PSi) synthesized by microwave plasma chemical vapor deposition (MPCVD). For the application, boron-doped and undoped diamond thin film has been performed and fabricated into an electrode device, and its microstructure, electrical and chemical properties have been studied. In order to enlarge the surface area of diamond electrodes, a negative bias was applied to the MPCVD process to deposit diamond thin film in a nano-structured form, so that its surface remained rough and nano-fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM. The morphology of boron-doped diamond thin films on PSi reveals nano-rods in the shape of diamond crystallites. Their electrochemical properties were evaluated by performing cyclic voltammetry (CV) measurement in inorganic K₄[Fe(CN)₆] in a K₂HPO₄ buffer solution. Boron-doped diamond thin film on PSi has demonstrated good electrochemical properties, with a larger redoxidation current of CV, due to its rough surface, which provides a more active electrochemical interface.     

Reduction products of graphite intercalation compounds with nickel and iron halides

The H₂ reduction of graphite intercalation compounds (GICs) with nickel and iron chlorides before and after fluorination with BrF₃ solutions in HF has been studied by X-ray diffraction, thermal analysis, and Raman scattering spectroscopy. The results indicate that, up to 700°C, the thermolysis of the GICs with nickel and iron chlorides does not reach completion. Thermolysis of the fluorinated GICs in a hydrogen atmosphere at 600°C can be used to fabricate metal-graphite composites. This behavior is interpreted in terms of the thermal properties of the GICs.     

Electrochemical and spectroscopic investigation of the reduction of dimethylglyoxime at mercury electrodes in the presence of cobalt and nickel

Voltammograms (polarograms) obtained from solutions of cobalt and nickel containing dimethylglyoxime (dmgH(2)) are widely used for the trace determination of these metals. Detailed electrochemical and spectroscopic studies on the reduction process observed in the analytically important ammonia buffer media at mercury dropping, hanging, and pool electrodes are all consistent with an overall 10-electron reduction process, in which both the dmgH(2) ligand and cobalt ions are reduced in the adsorbed state: Co(II) + 2dmgH(2) ? (solution) [Co(II)(dmgH)(2)] + 2H(+); [Co(II)(dmgH)(2)] + Hg ? (electrode) [Co(II)(dmgH)(2)](ads)Hg; and [Co(II)(dmgH)(2)](ads)Hg + 10e(-) + 10H(+) → Co(Hg) + 2[2,3-bis(hydroxylamino)butane]. The limited solubility of the nickel complex in aqueous media restricts the range of studies that can be undertaken with this system, but an analogous mechanism is believed to occur. Low-temperature voltammetric studies in dichloromethane at a frozen hanging mercury drop electrode and in situ electron spin resonance electrochemical measurements on more soluble analogues of the dimethylglyoxime complexes are consistent with an initial one-electron reduction step being available in the absence of water. Deliberate addition of water to acetone solutions enables the influence of the aqueous environment on voltammograms and polarograms to be examined. The results of the present study are compared with the wide range of mechanisms proposed in other studies.