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-BEHAVIOR OF YTTRIUM ION IN LICL-KCL-NACL EUTECTIC MELT

The electrochemical reduction of yttrium ion on a molybdenum electrode in a LiCl-KCl-NaCl eutectic melt at 723 K was found to be almost reversible and to proceed by a one-step three electron reaction. The diffusion coefficient D of the Y(III) ion was measured to be (3.3 +/- 0.4) x 10(-6) cm2 s-1 by cyclic voltammetry, (5.0 +/- 0.9) x 10(-6) cm2 s-1 by the rotating disk electrode method, and (7.1 +/- 0.7) x 10(-6) cm2 s-1 by chronopotentiometry. The D values obtained by the latter two methods are in fairly good agreement with each other. The rather low D value obtained by cyclic voltammetry might be attributed to the fact that yttrium metal can dissolve slightly in the chloride melt. The standard potential of Y(III)/Y(0) couple was determined to be (-3.174 +/- 0.006) V (vs. Cl2/Cl-) by open-circuit potentiometry, (-3.15 +/- 0.02) V (vs. Cl2/Cl-) by the rotating disk electrode method and (-3.16 +/- 0.02) V (vs. Cl2/Cl) by chronopotentiometry. These three values are in good agreement with each other. Several types of Ni-Y intermetallic compounds were found to be formed on a nickel electrode.

ELECTROCHEMICAL-BEHAVIOR OF N-METHYL-N'-HEXADECYLVIOLOGEN MONOLAYERS ON SILVER ELECTRODES - EFFECTS OF COUNTERIONS

N-Methyl-N'-hexadecylviologen (C16MV) has been the subject of several electrochemical and spectroelectrochemical studies which characterized the species present in various redox states for C16MV monolayers on silver electrode surfaces. Both self-assembled monolayers (SA) and Langmuir-Blodgett (LB) transferred systems have been studied. These indicated inconsistencies regarding the presence or absence of splitting of the first reduction peak in its cyclic voltammogram (CV). The present study demonstrates the important influence of the specific anionic species present in the supporting electrolyte. Splitting may or may not take place, depending on the size and relative strength of the adsorption of specific anions contributed by the supporting electrolyte. Small, strongly adsorbing anions such as iodide produced peak splitting in the CV of C16MV monolayers; bulky but weakly adsorbing anions such as perchlorate may disrupt the ordered structure of monolayers but produce no splitting. Ancillary data provided by surface enhanced Raman spectroscopy (SERS) was consistent with the electrochemical measurements.

DETERMINATION OF PARAMETERS OF FAST CHEMICAL REACTION OF ALIZARIN RED S BY SPECTROELECTROCHEMICAL METHOD WITH LOPTLC

The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.

Electrochemical measurement of hydrogen peroxide in plasma: Evaluation of freshwater prawn (Macrobrachium rosenbergii) and crucian carp (Cyprinus carpio) phagocytes under natural conditions

An electrochemical technique for the real-time detection of hydrogen peroxide (H2O2) was employed to describe respiratory burst activity (RBA) of phagocytes in plasma which can be used to evaluate the ability of immune system and disease resistance. The method is based upon the electric current changes, by redox reaction on platinum electrode of extracellular hydrogen peroxide (H2O2) released from phagocytes stimulated by the zymosan at 680 mV direct current (d.c.). Compared with the control, activation of respiratory burst by zymosan particles results in a high amperometric response, and a current peak was obtained during the whole monitoring process. The peak current was proved by addition Of Cu2+ and other controls, to be the result of intense release of H2O2 from phagocytes. The peak area was calculated and used to evaluate the quantity of effective H2O2, which represents the quantity of H2O2 beyond the clearance of related enzymes in plasma. According to Faraday's law, the phagocytes' ability of prawns to generate effective H2O2 was evaluated from 1.253 x 10(-14) mol/cell to 6.146 x 10(-14) mol/cell, and carp from 1.689 x 10(-15) Mol/Cell to 7.873 x 10(-1)5 mol/cell. This method is an acute and quick detection of extracellular effective H2O2 in plasma and reflects the capacity of phagocytes under natural conditions, which could be applied for selecting species and parents with high immunity for breeding in aquaculture. (c) 2007 Elsevier Ltd. All rights reserved.

Electrochemical, SEM/EDS and quantum chemical study of phthalocyanines as corrosion inhibitors for mild steel in 1 mol/l HCl

The inhibition effect of metal-free phthalocyanine (H2Pc), copper phthalocyanine (CuPc) and copper phthalocyanine tetrasulfuric tetrasodium salt (CuPc center dot S(4)center dot Na-4) on mild steel in I mol/l HCl in the concentration range of 1.0 X 10(-5) to 1.0 X 10(-3) mol/l was investigated by electrochemical test, scanning electron microscope with energy dispersive spectrometer (SEM/EDS) and quantum chemical method. The potentiodynamic polarization curves of mild steel in hydrochloric acid containing these compounds showed both cathodic and anodic processes of steel corrosion were suppressed, and the Nyquist plots of impedance expressed mainly as a capacitive loop with different compounds and concentrations. For all these phthalocyanines, the inhibition efficiency increased with the increase in inhibitor concentration, while the inhibition efficiencies for these three phthalocyanines with the same concentration decreased in the order Of CuPc center dot S(4)center dot Na-4 > CuPc > H2Pc according to the electrochemical measurement results. The SEM/EDS analysis indicated that there are more lightly corroded and oxidative steel surface for the specimens after immersion in acid solution containing 1.0 x 10(-3) mol/l phthalocyanines than that in blank. The quantum chemical calculation results showed that the inhibition efficiency of these phthalocyanines increased with decrease in molecule's LUMO energy, which was different from the micro-cyclic compounds. (c) 2005 Elsevier B.V. All rights reserved.

The study of oxygen spillover and back spillover on Pt/TiO2 by a potential dynamic sweep method

Oxygen spillover and back spillover on Pt/TiO2 catalysts have been studied by a potential dynamic sweep method. The characteristics of I-V profiles of Pt/TiO2 electrodes in the three potential sweep regions are different from those of Pt and TiO2 electrodes. The catalytic role of Pt/TiO2 in oxygen spillover and back spillover is identified. It decreases, and the electrochemical oxygen adsorption (or desorption) increases with elevating temperature of hydrogen post-treatment of Pt/TiO2; to a certain extent (hydrogen post-treatment of Pt/TiO2 at 700 degrees C), the control step of oxygen electrode process (anodic oxidation or cathodic reduction) changes from oxygen diffusion to electrochemical oxygen adsorption or desorption, respectively. Increasing the amount of Pt supported on TiO2 enhances the processes of oxygen spillover and back spillover. (C) 1999 Elsevier Science B.V. All rights reserved.

Electrochemical synthesis and characterization of conducting polyparaphenylene using room-temperature melt as the electrolyte

Freestanding polyparaphenylene films were obtained on polymerization of benzene at potential of 1.2 V versus Al wire on substrates like platinum/transparent conducting glass as an anode. The electrolyte used was chloroaluminate room-temperature melt, which was prepared by intimate mixing of a 1:2 ratio of cetyl pyridinium chloride and anhydrous aluminum chloride to yield a viscous liquid. This liquid was miscible in all proportions with benzene and other aromatic hydrocarbons in all proportions at room temperature. The polyparaphenylene films deposited on platinum anode exhibited a prominent cyclic voltammetric peak at 0.7 V versus Al wire as reference electrode in chloroaluminate medium. The impedance spectra gave low charge transfer resistance. The diffused reflectance electronic spectra of the film gave the peaks at 386 nm and 886 nm. The PPP films showed electronic conductivity around 3–4 × 104 S/cm by four probe method under nitrogen atmosphere. The polymer was also characterized by IR spectra, thermal studies, and SEM studies.

Probing Bias-Dependent Electrochemical Gas-Solid Reactions in (LaxSr1-x)CoO3-delta Cathode Materials

Spatial variability of bias-dependent electrochemical processes on a (La0.5Sr0.5)(2)CoO4 +/- modified (LaxSr1-x)CoO3- surface is studied using first-order reversal curve method in electrochemical strain microscopy (ESM). The oxygen reduction/evolution reaction (ORR/OER) is activated at voltages as low as 3-4 V with respect to bottom electrode. The degree of bias-induced transformation as quantified by ESM hysteresis loop area increases with applied bias. The variability of electrochemical activity is explored using correlation analysis and the ORR/OER is shown to be activated in grains at relatively low biases, but the final reaction rate is relatively small. At the same time, at grain boundaries, the onset of reaction process corresponds to larger voltages, but limiting reactivity is much higher. The reaction mechanism in ESM of mixed electronic-ionic conductor is further analyzed. These studies both establish the framework for probing bias-dependent electrochemical processes in solids and demonstrate rich spectrum of electrochemical transformations underpinning catalytic activity in cobaltites.

Physical and electrochemical evaluation of ATO supported IrO2 catalyst for proton exchange membrane water electrolyser

Antimony doped tin oxide (ATO) was studied as a support material for IrO₂ in proton exchange membrane water electrolyser (PEMWE). Adams fusion method was used to prepare the IrO₂-ATO catalysts. The physical and electrochemical characterisation of the catalysts were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder conductivity, cyclic voltammetry (CV) and membrane electrode assembly (MEA) polarisation. The BET surface area and electronic conductivity of the supported catalysts were found to be predominantly arisen from the IrO₂. Supported catalyst showed higher active surface area than the pristine IrO₂ in CV analysis with 85% H₃PO₄ as electrolyte. The MEA performance using Nafion®−115 membrane at 80 °C and atmospheric pressure showed a better performance for IrO₂ loading ≥60 wt.% than the pristine IrO₂ with a normalised current density of 1625 mA cm⁻² @1.8 V for the 60% IrO₂-ATO compared to 1341 mA cm⁻² for the pristine IrO₂ under the same condition. The higher performance of the supported catalysts was mainly attributed to better dispersion of active IrO₂ on electrochemically inactive ATO support material, forming smaller IrO₂ crystallites. A 40 wt.% reduction in the IrO₂ was achieved by utilising the support material.

The electrochemical reduction of 1-bromo-4-nitrobenzene at zinc electrodes in a room-temperature ionic liquid: a facile route for the formation of arylzinc compounds

The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC₆H₄NO₂) at zinc microelectrodes in the [C(₄)mPyrr][NTf₂] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC₆H₄NO₂ is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.

Voltammetric in situ measurements of heavy metals in soil using a portable electrochemical instrument

This paper presents a portable electrochemical instrument capable of detecting and identifying heavy metals in soil, in situ. The instrument has been developed for use in a variety of situations to facilitate contaminated land surveys, avoiding expensive and time-consuming procedures. The system uses differential pulse anodic stripping voltammetry which is a precise and sensitive analytical method with excellent limits of detection. The identification of metals is based on a statistical microprocessor-based method. The instrument is capable of detecting six different toxic metals (lead, cadmium, zinc, nickel, mercury and copper) with good sensitivity

Acidity compensation of electrochemical measurements for on-site monitoring of heavy metals

This paper presents an electrochemical instrumentation system capable of real-time in situ detection of heavy metals. A practical approach to introduce acidity compensation against changes in amplitude of the peak currents is also presented. The compensated amplitudes can then be used to predict the concentration level of heavy metals. The system uses differential pulse anodic stripping voltammetry, which is a precise and sensitive analytical method with excellent limits of detection. The instrument is capable of detecting lead, cadmium, zinc, nickel and copper with good sensitivity and precision. The system avoids expensive and time-consuming procedures and may be used in a variety of situations to help environmental assessment and control. 

Facile Synthesis of Anatase TiO2 Quantum-Dot/Graphene-Nanosheet Composites with Enhanced Electrochemical Performance for Lithium-Ion Batteries

A facile method to synthesize well-dispersed TiO₂ quantum dots on graphene nanosheets (TiO₂-QDs/GNs) in a water-in-oil (W/O) emulsion system is reported. The TiO₂/graphene composites display high performance as an anode material for lithium-ion batteries (LIBs), such as having high reversible lithium storage capacity, high Coulombic efficiency, excellent cycling stability, and high rate capability. The excellent electrochemical performance and special structure of the composites thus offer a way to prepare novel graphene-based electrode materials for high-energy-density and high-power LIBs. 

Electrochemical immunosensor for multiplexed detection of food-borne pathogens using nanocrystal bioconjugates and MWCNT screen-printed electrode

Bacterial food poisoning is an ever-present threat that can be prevented with proper care and handling of food products. A disposable electrochemical immunosensor for the simultaneous measurements of common food pathogenic bacteria namely Escherichia coli O157:H7 (E. coli), campylobacter and salmonella were developed. The immunosensor was fabricated by immobilizing the mixture of anti-E. coli, anticampylobacter and anti-salmonella antibodies with a ratio of 1:1:1 on the surface of the multiwall carbon nanotube-polyallylamine modified screen printed electrode (MWCNT-PAH/SPE). Bacteria suspension became attached to the immobilized antibodies when the immunosensor was incubated in liquid samples. The sandwich immunoassay was performed with three antibodies conjugated with specific nanocrystal ( -E. coli-CdS, -campylobacter-PbS and -salmonella-CuS) which has releasable metal ions for electrochemical measurements. The square wave anodic stripping voltammetry (SWASV) was employed to measure released metal ions from bound antibody nanocrystal conjugates. The calibration curves for three selected bacteria were found in the range of 1 × 103 – 5 × 105 cells mL−1 with the limit of detection (LOD) 400 cells mL−1 for salmonella, 400 cells mL−1 for campylobacter and 800 cells mL−1 for E. coli. The precision and sensitivity of this method show the feasibility of multiplexed determination of bacteria in milk samples.