Cyclic voltammetric and in situ Fourier transform infrared spectroelectrochemical studies on the reaction of Cd2+ on the plussian blue/platinum modified electrode

Plussian blue(PB)/Pt modified electrode Tvas studied in the CdCl2 electrolyte solution by cyclic voltammetry and in situ FTIR spectroelectrochemistry. It was found that Cadmium ion was capable of substituting the high-spin iron of PB in an electrochemically induced substitution reaction and hexacyanoferrate cadmium (CdHCF) can be formed in the PB film. But PB and CdHCF in mixture film showed their own electrochemistry properties without serious effect on each other. The mechanism of substitution reaction has been given in detail.

In-situ FTIR spectroelectrochemical study of chromium hexacyanoferrate on glassy carbon electrode

Chromium hexacyanoferrate (CrHCF) modified grassy carbon electrode (GC) in different electrolytes was studied by cyclic voltammetry and in situ FTIR spectroelectrochemistry. The results indicate that the behavior of CrHCF firm can be understood in term of two structures: Cr1/3Cr(III)Fe(II)(CN), and MCr(III)Fe(II)(CN)(6). Besides,the film exists in amorphous state: the outer layer is porous film, while the inner layer is relatively compact. According to the electrochemical reaction of CrHCF, the lattice can contract and expand with the cations' diffusion.

In-situ microscopic FTIR spectroelectrochemical study of the reduction of K3Fe(CN)(6) in polymer electrolyte

Cyclic voltammetry and in-situ microscopic FTIR spectroelectrochemistry were used for the electrochemical and vibrational characterizations of the reduction process of K3Fe (CN)(6) in polyethylene glycol(PEG) with LiClO4 as supporting electrolyte at a Pt microelectrode. The rate of electron transfer is a function of the concentration of the supporting electrolyte. The redox potentials and cyclic voltammetric currents vary with Li/O molar ratio. The bl-situ spectroelectrochemistry shows that the infrared spectra are influenced by the concentration of LiClO4. The bridging cyanide groups with a structure Fe-I-C drop N ... Fe-I-C drop N are formed during the reduction process of K3Fe (CN)(6). There may be an activated complex between the Lif cation and the complex anion.

Axial coordination effects of pyridine on the electrochemistry of (TPP)Co in 1,2-dichloroethane solution

The electrochemistry of (TPP)Co in the presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. With the addition of pyridine to the solution, the reduction peaks of the axial complex compounds, (TPP)Co(III)(Py) and (TPP)Co(III)(Py)(2) were observed. It was found that the reduction peak of Co(II)/Co(I) shifted to about -1.20V (SCE) with the increase of added pyridine. The new reduction peak may be attributed to the direct reduction of the axially complex (TPP)Co(II)(Py).

In-situ FTIR spectroelectrochemical investigation of cobalt(II)-cyanoferrate polymeric film coated on a glassy carbon electrode

Cobalt(II)-cyanoferrate polymeric film has been electrochemically deposited on a glassy carbon electrode and investigated by cyclic voltammetry and in-situ reflection FTIR spectroscopy. A reorientation of the terminal C=N groups upon redox reactions was proposed. The stretching vibration mode of the terminal C=N groups associated with Fe(III) was observed at 2122 cm(-1), however, the stretching vibration mode for terminal groups associated with Fe(II) did not appear. This process could result in a switch between lattice-closed and lattice-opened surface structure. (C) 1997 Elsevier Science B.V.

In situ external reflection FTIR spectroelectrochemical investigation of poly(o-phenylenediamine) film coated on a platinum electrode

The electrochemically deposited poly(o-phenylenediamine) film on a Pt electrode has been investigated utilizing in situ external reflection FTIR spectroelectrochemistry technique. The prepared ladder polymer film is found to be partially ring-opened. The dopant ClO4- is evidenced to orient in such a way that more than one oxygen atom attach to the charge sites of the polymer. This suggests that positive charges of oxidized polymer are partially delocalized over the whole chains. The proton movement observed during the oxidation reaction is associated with the solvated MeCN molecule. It is proposed that the proton diffusion, dissolvation and protonation of the film may be essential to the electrochemical reduction reaction of the film. Copyright (C) 1996 Elsevier Science Ltd.

Orientation and electrocatalysis of riboflavin adsorbed on carbon substrate surfaces

Based on scanning tunnelling microscopy and electrochemical measurements, orientation and electrocatalytic function of riboflavin adsorbed on carbon substrates have been described for the first time. Scanning tunnelling micrographs show clearly that tip induction may result in an orientation change of the adsorbed riboflavin molecule on highly oriented pyrolytic graphite from the initially vertical orientation to the stable flat form. The adsorbed riboflavin as an effective mediator can accelerate the reduction of dioxygen which accepts two electrons from the reduced riboflavin to generate hydrogen peroxide. The rate constants of the electrocatalytic reaction in various pH solutions were determined using a rotating disc electrode modified with riboflavin. The pH effect and possible catalytic mechanism are discussed in detail.

Effect of water on the electrochemical oxidation process of biliverdin in dimethylformamide

A systematic study has been made for the electrochemical oxidation reaction of biliverdin (BV) in pure dimethylformamide (DMF) and in DMF - H2O mixed solvent by in situ time resolved spectroelectrochemical and cyclic voltametric techniques. The experiments show that not only the oxidation of BV is promoted, the reaction mechanism is also changed from a ECEC to a ECCECC process by the introduction of water into DMF.

ELECTROCHEMICAL REDUCTION PROCESS OF BILIRUBIN IN DIMETHYLFORMAMIDE

The electrochemical reduction behavior of bilirubin (BR) at platinum electrode in DMF was investigated by cyclic voltammetry, in situ electron spin resonance spectroscopy and in situ rapid scanning thin layer spectroelectrochemistry. Experimental results revealed that the reduction of BR firstly undergoes an ECE process: GRAPHICS The generated (BR)(2)(3-). can be re-oxidized to BR and then to purpurin (Pu) by a series of oxidation processes: GRAPHICS However, the re-reduction reactions of Pu are not the reverse processes. The different reduction mechanisms are discussed in detail.

ELECTROCHEMISTRY AND IN-SITU IR MICROSPECTROELECTROCHEMISTRY IN A VERSATILE THIN-LAYER REFLECTION FOURIER-TRANSFORM IR MICROSPECTROELECTROCHEMICAL CELL

A simple, convenient and versatile thin layer reflection Fourier transform IR microspectroelectrochemical (FTIRMSEC) cell has been described and characterized. Electrochemistry and in situ FTIR microspectroscopy were studied by using the hexacyanoferrate redox couple in aqueous sulphate solution, indicating that this type of cell is characteristic of both micro- or ultramicroelectrode and thin layer spectroelectrochemistry. Furthermore, the application of this FTIRMSEC cell to IR for characterization of the products of electrochemical reactions was carried out for the oxidation of (mesotetraphenylporphinato)manganese(III) perchlorate in dichloromethane + tetrabutylammonium perchlorate solution. Finally, the advantages and problems of this type of cell compared with a conventional optically transparent thin layer FTIR spectroelectrochemical cell were discussed.

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

Characterization of 1:12 Phosphomolybdic Anions Doped Polypyrrole (PMo12/PPy) Film Electrode

1:12 phosphomolybdic anion doped polypyrrole film electrode was characterized by in-situ UV-vis spectroelectrochemistry, X-ray photoelectron spectroscopy(XPS), scan electronic microscopy(SEM) and electron spin resonance(ESR) spectroscopy.

ELECTROCHEMICAL AND IN-SITU SPECTROELECTROCHEMICAL STUDY OF (TETRAPHENYLPORPHINATO)MANGANESE(III) PERCHLORATE IN THE PRESENCE OF CHLORIDE ANIONS .2. OXIDATION PROCESSES

An investigation of electrode oxidation processes of (tetra-phenylporphinato) manganese (III) Perchlorate, (TPS)Mn(III)ClO4, was carried out during the titration of chloride anions by conventional cyclic voltammetry, thin-layer cyclic voltammetry and spectroelectrochemistry. It was demonstrated that in the presence of one equivalent amount of Cl-, the first one electron oxidation reaction corresponds to the Mn(III)I cation radical oxidation, and the second one electron oxidation corresponds to the cation radical/dication generation followed by an iso-porphyrin formation reaction, however in the presence of two equivalent amount of Cl-, the first one electron oxidation of Mn(III) gives Mn(IV) porphyrin and the second one electron oxidation generates cation radicals of Mn(IV) followed by an iso-porphyrin formation reactions. Mechanisms of these redox processes are postulated.

STUDY OF THE ELECTRODE PROCESS OF HEMOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode is reported. The resulting film on a platinum electrode surface was analyzed with electron spectroscopy for chemical analysis (ESCA). The heterogeneous electron transfer processes of hemoglobin at the polymerized azure A film electrode have been investigated using in situ UV-visible spectroelectrochemistry. The formal potential (E-degrees') and electron transfer number (n) of hemoglobin were calculated as E = 0.088 V versus NHE (standard deviation +/- 0.5, N = 4) and n = 1.8 (standard deviation +/- 0.5, N = 4). Exhaustive reduction and oxidation electrolysis are achieved in 80 and 380 seconds, respectively, during a potential step between -0.3 and +0.3 V. A formal heterogeneous electron-transfer rate constant (k(sh)) of 3.54(+/- 0.12) X 10(-6) cm/s and a transfer coefficient (alpha) of 0.28(+/- 0.01) were obtained by cyclic voltabsorptometry, which indicated that the poly-azure A film electrode is able to catalyze the direct reduction and oxidation of hemoglobin.

STUDY ON ELECTRODE PROCESS OF MYOGLOBIN AT A POLYMERIZED AZURE A FILM ELECTRODE

The electrochemically polymerized azure A film electrode was firstly reported in this paper. A quasi-reversible electrode processes of myoglobin with the formal heterogeneous electron transfer rate constant (k(sh)) of 1.73 x 10(-4) cm.s-1 at the polymerized azure A modified electrode have been achieved using in-situ UV-visible spectroelectrochemistry. The adsorption of myoglobin on the polymerized azure A film electrode surface was confirmed by XPS. With simultaneously studying of cyclic voltammetry and in-situ cyclic voltabsorptometry, the attribution of the voltammetry responses of myoglobin at the film electrode has been studied. The mechanism for the heterogeneous electron transfer of myoglobin at the polymerized azure A film modified electrode has been proposed as well.