Multilayer assemblies consisting of tri-vanadium-substituted heteropolyanions and its electrocatalytic properties

We describe the controlled fabrication of ultrathin multilayer films consisting of tri-vanadium- substituted heteropolytungstate anions (denoted as P2W15V3) and a cationic polymer of quaternized poly (4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) (denoted as QPVP-Os) on the 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) surface based on layer-by-layer assembly. Cyclic voltammetry and UV-vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus-formed multilayer films. The V-centered redox reaction of P2W15V3 in the multilayer films can effectively catalyze the reduction of BrO3- and NO2-. The resulting P2W15V3/QPVP-Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO3- and NO2-, and the catalytic oxidation of ascorbic acid.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

The nature of the interaction between polyaniline and 2,5-dimercapto-1,3,4-thiadiazole in electrochemical redox processes

The interaction between polyaniline (PAn) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was investigated by means of cyclic voltammetry and UV-visible spectroscopy. The results show that the polymerization-depolymerization reaction of DMcT or its dilithium salt Li(2)DMcT is a kinetically quasi-reversible process. PAn exhibits very weak electrochemical activity in neutral propylene carbonate. After doping with protonic acid, such as hydrochloric acid or maleic acid etc., however, it shows an extensively enhanced electroactivity. For the complex system, PAn-DMcT or PAn-Li(2)DMcT, polyaniline has no catalytic activity for the electrochemical polymerization-depolymerization reaction of DMcT or DMcT(2-). Instead, the enhancement of the electrochemical redox activity of PAn-DMcT system compared with that of PAn, DMcT, Li(2)DMcT, and PAn-Li(2)DMcT comes from the protonic doping of PAn by DMcT.

PMo12-doped carbon ceramic composite electrode based on sol-gel chemistry and its electrocatalytic reduction of bromate

A conductive carbon ceramic composite electrode (CCE) comprised of cc-type 1:12 phosphomolybdic acid (PMo12) and carbon powder in an organically modified silicate matrix was fabricated using a sol-gel method and characterized by scanning electron microscopy, cyclic voltammetry, and Osteryoung square-wave voltammetry. Osteryoung square-wave voltammograms of the modified electrode immersed in different acidic aqueous solutions present the dependence of current and redox potential on pH. The PMo12-doped CCE shows more reversible reaction kinetics, good stability and reproducibility, especially the renewal repeatability by simple polishing in the event of surface fouling or dopant leaching. Moreover, the modified electrode shows good catalytic activity for the electrochemical reduction of bromate.

Electrochemical and quartz crystal microbalance study for the electrochemical oxidation of 2-mercaptobenzimidazol

With the cyclic voltammetry and quartz crystal microbalance (QCM), the oxidation process and the electrodeposition behavior were studyied during the electrochemical oxidation of 2-mercaptobenzimidazol in aqueous solution. The E-pH diagram was also gained. These results showed the oxidation reaction was one electron reaction. The results from X-ray photoelectron spectrometry verified that the 2-mercaptobenzimidazol was oxidized to bisbenzimidazoyl disulfide.

Covalent modification of a glassy carbon surface by 4-aminobenzoic acid and its application in fabrication of a polyoxometalates-consisting monolayer and multilayer films

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy measurement proves the presence of 4-carboxylphenylamine monolayer on the GCE. The redox responses of various electroactive probes were investigated on the 4-ABA-modified GCE. Electron transfer to Fe(CN)(6)(3-) in solutions of various pHs was studied by both cyclic voltammetry and electrochemical impedance analysis on the modified electrode. Changes in the solution pH value result in the variation of the terminal group charge state, based on which surface pK(a) values are estimated. The 4-ABA-modified GCE was used as a suitable charged substrate to fabricate polyoxometalates-consisting (POM-consisting) monolayer and multilayer films through layer-by-layer assembly based on electrostatic attraction. Cyclic voltammetry shows the uniform growth of these three-dimensional multilayer films. Taking K10H3[Pr-(SiMo7W4O39)(2)]. H2O (abbreviated as Pr(SiMo7W4)(2)), for example, the preparation and electrochemical behavior of its monolayer and multilayer film had been investigated in detail. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the 4-ABA-modified GCE.

Electrocatalytic reduction of O-2 and H2O2 at the glass carbon electrode modified with microperoxidase-11

Electrocatalytic reduction of O-2 and H2O2 at the glass carbon electrode modified with microperoxidase-11 immobilized with Nafion film has been studied by means of cyclic voltammetry and rotating disk electrode techniques. The modified electrode shows high catalytic activity toward the reduction of both O-2 and H2O2. The rate constants of Oz and H2O2 reduction at the modified electrode have been measured and compared. It is found that O-2 undergoes a four-electron reduction at the modified electrode and the catalytic activity for the reduction of O-2 is dependent on the pH of the solutions.

Synthesis and free-radical ring opening polymerization of macrocyclic aryl thioether ether ketone (sulfone) oligomers

Two kinds of novel macrocyclic aryl thioether ether oligomers were synthesized by nucleophilic condensation reaction in high yields under pseudo-high-dilution condition. A combination of H-1 NMR, GPC and MALDI-TOF MS analyses unambiguously confirmed the cyclic nature and their distributions, Macrocyclic thioether ether ketone oligomers can undergo facile melt ring opening polymerization(ROP) initiated by thiyl radical to give a high molecular weight polymer.

Fabrication of nanometer-sized electrodes and tips for scanning electrochemical microscopy

A novel method for fabrication of nanometer-sized electrodes and tips suitable for scanning electrochemical microscopy (SECM) is reported. A fine etched Pt wire is coated with polyimide, which was produced by polymerization on the Pt surface initiated by heat. This method can prepare electrodes with effective radii varying from a few to hundreds of nanometers. Scanning electron microscopy, cyclic voltammetry, and SECM were used to characterize these electrodes. Well-defined steady-state voltammograms could be obtained in aqueous or in 1,2-dichloroethane solutions. Ibis method produced the nanoelectrodes with exposed Pit on the apex, and they can also be employed as the nanotips for SECM investigations. Different sizes of Pt nanotips made by this method were employed to evaluate the kinetics of the redox reaction of Ru(NH3)6(3+) on the surface of a large Pt electrode by SECM, and the standard rate constant kappa (o) of this system was calculated from the best fit of the SECM approach curve. This result is similar to the values obtained by analysis of the obtained voltammetric data.

Multilayer assemblies of tungstodiphosphate anions on 1,7-diaminoheptane modified glassy carbon electrode and the electrocatalytic reduction to iodate

1,7-Diaminoheptane (DAH) had been covalently grafted on glassy carbon electrode by amino cation radical formation, which resulted in a stable cationic monolayer under proper pH conditions. Dawson-type tungstodiphosphate anion, P2W18O626- and small molecule, Ru(NH3)(6)(3+) were alternately assembled on the DAH modified electrode through layer-by-layer electrostatic interaction. Thus-prepared multilayer film had been characterized by cyclic voltammetry and X-ray photoelectron spectroscopy. The P2W18O626- multilayers exhibit high electrocatalytic response and sensitivity towards the reduction of iodate. With the increase of the number of P2W18O626- the catalytic current was enhanced and the catalytic potential shifted positively. Iodate in table salt was determined at the modified electrode containing three layers of P2W18O626- with satisfactory results. The multilayer electrode is promising as an electrochemical sensor for the detection of trace iodate.

Electrochemical and spectroscopic study of vitamin D-2 by in situ thin layer CD spectroelectrochemistry

The electrooxidation of vitamin D-2 (VD2) was studied by cyclic voltammetry and in situ circular dichroic (CD) spectroelectrochemistry for the first time, The mechanism of electrooxidation and some useful kinetic and adsorption parameters were obtained. The results showed that the oxidation of VD2 in ethanol solution is an irreversible diffusion controlled process following a weak adsorption of the electroinactive product at a glassy carbon electrode, which blocks the electrochemical reaction. The electrooxidation occurs mainly at the triene moieties of the VD2 molecule. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E-0 = 1.08 V, alphan = 0.245, the standard electrochemical rate constant k(0) = 4.30( +/- 0.58) x 10(-4) cm s(-1) and the adsorption constant beta = 1.77(+/- 0.25) were obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

Electrochemical and in situ spectroelectrochemical behavior of 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and (Zn(II)OHTTAP)

The characterization of free base porphyrin 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and its zinc(II) complexes [Zn(II)OHTTAP] containing eight thioether groups at the beta -pyrrole positions of the macrocycle was reported. Results obtained by cyclic voltammetry and differential pulse voltammetry indicated a five-electron reduction in five steps for each complex. They were oxidized in two single-electron-transfer steps to yield pi -cation radicals and dications and reduced in three single-electron-transfer steps to yield pi -anion radicals, dianions and trianions, respectively. The redox property of H(2)OHTTAP was unusual as compared to porphyrins (PPs) and phthalocyanines (Pcs). Each process was monitored by in situ thin-layer spectroelectrochemistry, which indicated that only the Ligand was electroactive. The existence of the eight hexylthio groups was responsible for the intrastack interactions and enhanced intracolumnar and intercolumnar electron motions, resulting in improved conductivity. Copyright (C) 2001 John Wiley & Sons, Ltd.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Synthesis and properties of three tris(1,10-phenanthroline) ruthenium (II) derivatives

Three new asymmetrical ruthenium (II) complexes: [Ru(phen)(2){phen-NHCO(CH2)(4)Br}](PF6)(2), [Ru(phen)(2){phen-NHCO(CH2)(5)Br}](PF6)(2) and [Ru(phen)(2){phen-NHCO(CH2)(10)Br}](PF6)(2) were synthesized, which were confirmed by the technique of FT-IR, H-1 NMR and ESI-MS. The electrochemical and fluorescent properties of three Ru (II) complexes were investigated with cyclic voltammetry and fluorometry.

Technique for determination of gold electrode area and its application of characterization in self-assembling process

Underpotential deposition(UPD) of copper at polycrystal gold surface under different concentrations has been studied, and its reversibility and stability in high concentration (0.2M CuSO4+0.IM H2SO4) have been demonstrated by cyclic voltermmetry and EQCM. A Valid approach to determine the gold electrode area in presence of adsorbed species has been provided by using Cu UPD method. Further, the growth kinetics of decane thiol on gold has also been investigated based on such a Cu UPD technique.