Sol-gel-derived, polishable, 1 : 12-phosphomolybdic acid-modified ceramic-carbon electrode and its electrocatalytic oxidation of ascorbic acid

Novel ceramic-carbon electrodes (CCEs) containing 1:12-phosphomolybdic acid (PMo12) were constructed by homogeneously dispersing PMo12 and graphite powder into methyltrimethoxysilane-derived gel. Peak currents for the PMo12-doped CCE were surface-controlled at lower scan rates but diffusion-controlled at higher scan rates and peak potentials shifted to the negative potential direction with increasing pH. In addition, the electrode exhibited electrocatalytic activity toward the oxidation of ascorbic acid. The PMo12-modified CCE presented good chemical and mechanical stability and good surface renewability (ten successive polishing resulted in less than 5% relative standard deviation). (C) 2000 Elsevier Science B.V. All rights reserved.

AMPEROMETRIC DETECTION OF CATECHOLAMINES WITH LIQUID-CHROMATOGRAPHY AT A POLYPYRROLE-PHOSPHOMOLYBDIC ANION-MODIFIED ELECTRODE

A conducting polypyrrole film immobilized with PMo12O403- anion on a glassy carbon electrode was prepared by an electrochemical method. This kind of chemically modified electrode (CME) was prepared successfully by doping the polypyrrole film electrode wit

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.

STUDY OF A 1/12 PHOSPHOMOLYBDIC ANION DOPED POLYPYRROLE FILM ELECTRODE AND ITS CATALYSIS

A phosphomolybdic anion doped polypyrrole (PMo12O403- + PPy) film electrode has been prepared by electrochemical polymerization of pyrrole in an aqueous solution of 0.5 mol l-1 H2SO4 or 0.5 mol l-1 KNO3 containing PMo12O403- anions, and characterized by scanning electron microscopy and in-situ UV-visible spectroelectrochemical methods. The film electrode obtained is very stable upon potential cycling in acidic solution, but not in neutral solution. The catalytic effect of the film electrode on the reduction of ClO3- and BrO3- was studied.

RESEARCHES ON CHEMICALLY MODIFIED ELECTRODES - ELECTROCHEMISTRY OF 1-12 PHOSPHOMOLYBDIC HETEROPOLY ANION FILM MODIFIED ELECTRODE

A monolayer of 1:12 phosphomolybdic anion (PMo_(12)) was modified electrochemically on a glassy carbon electrode and its electrochemical behavior was studied with cyclic voltammetry (CV). It is shown that PMo_(12) film is adsoibed strongly on the surface of glassy carbon electrodes, H~+ ions in the solution plays an important role in the electrochemical processes of PMo_(12) film modified electrodes, whereas other anions, such as Cl~-, NO_3~-, SO_4~(2-), ClO_4~- and PO_4~(3-) etc., do not take par...

Determination of phosphorus in biodiesel using 1:12 phosphomolybdic modified electrode by cyclic voltammetry

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PVA-SSA-HPA Mixed-Matrix-Membrane Electrolytes for DMFCs

Stabilized forms of heteropolyacids (HPAs), namely phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA), are incorporated into poly (vinyl alcohol) (PVA) cross-linked with sulfosuccinic acid (SSA) to form mixed-matrix membranes for application in direct methanol fuel cells (DMFCs). Bridging SSA between PVA molecules not only strengthens the network but also facilitates proton conduction in HPAs. The mixed-matrix membranes are characterized for their mechanical stability, sorption capability, ion-exchange capacity, and wetting in conjunction with their proton conductivity, methanol permeability, and DMFC performance. Methanol-release kinetics is studied ex situ by volume-localized NMR spectroscopy (employing point-resolved spectroscopy'') with the results clearly demonstrating that the incorporation of certain inorganic fillers in PVA-SSA viz., STA and PTA, retards the methanol-release kinetics under osmotic drag compared to Nafion, although PVA-SSA itself exhibits a still lower methanol permeability. The methanol crossover rate for PVA-SSA-HPA-bridged-mixed-matrix membranes decreases dramatically with increasing current density rendering higher DMFC performance in relation to a DMFC using a pristine PVA-SSA membrane. A peak power density of 150 mW/cm(2) at a load current density of 500 mA/cm(2) is achieved for the DMFC using a PVA-SSA-STA-bridged-mixed-matrix-membrane electrolyte. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3465653] All rights reserved.

Sodium-alginate-based proton-exchange membranes as electrolytes for DMFCs

Novel mixed-matrix membranes prepared by blending sodium alginate (NaAlg) with polyvinyl alcohol (PVA) and certain heteropolyacids (HPAs), such as phosphomolybdic acid (PMoA), phosphotungstic acid (PWA) and silicotungstic acid (SWA), followed by ex-situ cross-linking with glutaraldehyde (GA) to achieve the desired mechanical and chemical stability, are reported for use as electrolytes in direct methanol fuel cells (DMFCs). NaAlg-PVA-HPA mixed matrices possess a polymeric network with micro-domains that restrict methanol cross-over. The mixed-matrix membranes are characterised for their mechanical and thermal properties. Methanol cross-over rates across NaAlg-PVA and NaAlg-PVA-HPA mixed-matrix membranes are studied by measuring the mass balance of methanol using a density meter. The DMFC using NaAlg-PVA-SWA exhibits a peak power-density of 68 mW cm(-2) at a load current-density of 225 mA cm(-2), while operating at 343 K. The rheological properties of NaAlg and NaAlg-PVA-SWA viscous solutions are studied and their behaviour validated by a non-Newtonian power-law.

Chitosan/heteropolyacid composite membranes for direct methanol fuel cell

As inorganic proton conductors. phosphomolybdic acid (PMA), phosphotungstic acid (PWA) and silicotungstic acid (SiWA) are extremely attractive for proton-conducting composite membranes. An interesting phenomenon has been found in our previous experiments that the mixing of chitosan (CS) solution and different heteropolyacids (HPAs) leads to strong electrostatic interaction to form insoluble complexes. These complexes in the form of membrane (CS/PMA, CS/PWA and CS/SiWA composite membranes) have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Therefore, HPAs can be immobilized within the membranes through electrostatic interaction, which overcomes the leakage problem from membranes.

Characterization of organic-inorganic multilayer films by cyclic voltammetry, UV-Vis spectrometry, X-ray photoelectron spectroscopy, small-angle X-ray diffraction and electrochemical impedance spectroscopy

We have employed several techniques, including cyclic voltammetry, UV-Vis spectrometry, small-angle X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy, to characterize the formation processes and interfacial features of ultrathin multilayer films of silicotungstate and a cationic redox polymer on cysteamine-coated Au electrodes self-assembled monolayers. All of these techniques confirm that the multilayer films are built up stepwise as well as uniformly in a layer-by-layer fashion. In particular, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes. It has been proved that the electrochemical impedance spectroscopy is a very useful technique in characterization of multilayer films because it provides valuable information about the interfacial impedance features.

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.

Comparative studies on electrochemical behavior and electrocatalytic properties of heteropolyanion-containing multilayer films prepared by two methods

Two modification methods for multilayer formation, i.e. immersion growth and electrochemical growth, were studied comparatively for their influence on the electrochemical behavior and the electrocatalytic properties of the thus-fabricated SiMo11V-containing multilayer films. Electrochemical growth was proven to be a more suitable method than immersion growth in preparing uniform ultrathin multilayer self-assemblies with good functions. We investigated the effects of scan rate and pH on the electrochemical behavior of the monolayer and multilayer films. We also compared the electrocatalytic effects on the reduction of BrO3- and HNO2 by the multilayer films prepared by the two methods. Moreover, the influence of multilayer thickness and the identity of the outermost layer on the electrocatalytic properties were studied. Much higher catalytic currents appeared on the thicker multilayer films than those on the thinner ones. On the other hand, the catalytic currents became smaller when the multilayer films with SiMo11V as the outermost layer were covered with an additional quarternized poly(4-vinylpyridine) layer partially complexed with osmium bis(2,2'-bypyridine) chloride (QPVP-Os layer). These influences were believed to be due to the different quantities of electrocatalyst loaded in the multilayer films and the blocking effect of the QPVP-Os outermost layer. (C) 2000 Elsevier Science S.A. All rights reserved.

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 growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.