ELECTRODEPOSITION OF PLATINUM PARTICLES ON GLASSY-CARBON MODIFIED WITH COBALT PORPHYRIN AND NAFION FILM AND THEIR ELECTROCATALYTIC REDUCTION OF DIOXYGEN

In this paper, five types of chemically modified electrode (CMEs) prepared with the deposition of platinum particles on various surfaces of glassy carbon (GC) modified with cobalt porphyrin and Nafion(R) solution are characterized using the electron scanning microscope (SEM). Their activities in the four-electron reduction of dioxygen to water on the basis of their electrochemical data from cyclic voltammetric and rotating ring-disk electrode (RRDE) experiments are examined and compared. Platinum particles dispersed on the GC surface adsorbed with the cobalt porphyrin exhibit the highest activity for the electrocatalytic reduction of dioxygen. However it is interesting that the cobalt ion is lost from the center of the porphyrin ring during the preparation of the cobalt porphyrin + Nafion mixture solution, while the porphyrin ring still remains in the Nafion film, as shown by EDX analysis. The incorporation of the porphyrin may change the structure of the Nafion film into a looser form, since the platinum particles dispersed in the film are more readily exposed, resulting in more favourable mass transfer and higher activity for the electrocatalytic reduction of dioxygen.

INVESTIGATION OF MICROSTRUCTURE AT IRON TETRAPHENYLPORPHYRIN MODIFIED CLASSY CARBON ELECTRODE BY XPS

Microstructure of the glassy carbon surface modified with iron tetraphenyfporphyrin (FeTPP) by heat treatment has been studied by XPS,, DTA and TG. XPS spectra of Fe 2P_3\2 level in FeTPP and iron tetraphenylporphyriu/glassy carbon (FeTPP/GC) have shown that a bond can be formed between the glassy carbon surface and both the central metal iron ion and the macrocyclic, ligand, which loses its four phenyl groups during the beat treatment. The relationship between the surface mierostructure of FeTPP/GC and the...

Electrochemical Detection of Hydrazine Based on Electrospun Palladium Nanoparticle/Carbon Nanofibers

In this work, we developed an electrochemical method for the detection of hydrazine based oil palladium nanoparticle/carbon nanofibers (Pd/CNFs). Pd/CNFs were prepared by electrospinning technique and subsequent thermal treatments. The electrocatalytic behaviors of Pd/CNFs modified glassy carbon electrode (Pd/CNF-GCE) for hydrazine oxidation were evaluated by cyclic voltammetry (CV), an obvious and well-defined oxidation peak appeared at -0.32 V (vs. Ag/AgCl). The mechanism of the oxidation of hydrazine at Pd/CNF-GCE was also studied, which demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. Furthermore, the wide linear range, low detection limit, good reproducibility and excellent storage stability were obtained utilizing differential pulse voltammetry (DPV).

Direct electrochemistry of glucose oxidase and biosensing for glucose based on carbon nanotubes@SnO2-Au composite

Multiwalled carbon nanotubes@SnO2-Au (MWCNTs@SnO2-Au) composite was synthesized by a chemical route. The structure and composition of the MWCNTs@SnO2-Au composite were confirmed by means of transmission electron microscopy, X-ray photoelectron and Raman spectroscopy. Due to the good electrocatalytic property of MWCNTs@SnO2-Au composite, a glucose biosensor was constructed by absorbing glucose oxidase (GOD) on the hybrid material. A direct electron transfer process is observed at the MWCNTs@SnO2-Au/GOD-modified glassy carbon electrode. The glucose biosensor has a linear range from 4.0 to 24.0 mM, which is suitable for glucose determination by real samples. It should be worthwhile noting that, from 4.0 to 12.0 mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations in human blood. Meanwhile, the resulting biosensor can also prevent the effects of interfering species.

Carbon Nanotube/Silica Coaxial Nanocable as a Three-Dimensional Support for Loading Diverse Ultra-High-Density Metal Nanostructures: Facile Preparation and Use as Enhanced Materials for Electrochemical Devices and SERS

In this paper, we have reported a very simple strategy (combined sonication with sol-gel techniques) for synthesizing well-defined silica-coated carbon nanotube (CNT) coaxial nanocable without prior CNT functionalization. After functionalization with NH2 group, the CNT/silica coaxial nanocable has been employed as a three-dimensional support for loading ultra-high-density metal or hybrid nanoparticles (NPs) such as gold NPs, Au/Pt hybrid NPs, Pt hollow NPs, and Au/Ag core/shell NPs. Most importantly, it is found that the ultra-high-density Au/Pt NPs supported on coaxial nanocables (UASCN) could be used as enhanced materials for constructing electrochemical devices with high performance. Four model probe molecules (O-2, CH3OH, H2O2, and NH2NH2) have been investigated on UASCN-modified glassy carbon electrode (GCE). It was observed that the present UASCN exhibited high electrocatalytic activity toward diverse molecules and was a promising electrocatalyst for constructing electrochemical devices with high performance. For instance, the detection limit for H2O2 with a signal-to-noise ratio of 3 was found to be 0.3 mu M, which was lower than certain enzyme-based biosensors.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in sol-gel-derived ceramic-carbon nanotube nanocomposite film

The sol-gel-derived ceramic-carbon nanotube (SGCCN) nanocomposite film fabricated by doping multiwall carbon nanotubes (MWNTs) into a silicate get matrix was used to immobilize protein. The SGCCN film can provide a favorable microenvironment for horseradish peroxidase (HRP) to perform direct electron transfer (DET) at glassy carbon electrode. The HRP immobilized in the SGCCN film shows a pair of well-defined redox waves and retains its bioelectrocatalytic activity to the reduction of O-2 and H2O2, which is superior to that immobilized in silica sol-gel film.

Fabrication and characterization of SERS-active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4-aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS-based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80-100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 x 10(4) relative to silver colloid, which might have resulted from the presence of 'hot-spots' at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 x 10(7) by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface.

Self-assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surf ace-enhanced Raman scattering (SERS) substrate by self-assembled silver nanoparticles on a monolayer of 4-aminophenyl-group-modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4-aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping-mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p-aminothiophenol (p-ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10(-9) m. This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon-based materials for SERS with high sensitivity.

Preparation of a phosphopolyoxomolybdate P2Mo18O626- doped polypyrrole modified electrode and its catalytic properties

A phosphopolyoxomolybdate (P2Mo18) doped polypyrrole (PPy) modified electrode was prepared in aqueous solution by a one-step method. During the polymerization of PPy, P2Mo18 acted as both catalyst and dopant. The electrochemical behavior of the PPy/P2Mo18 modified electrode before and after the overoxidation of PPy was investigated. Both of these showed a catalytic effect toward bromate. The PPy/P2Mo18 composite film was characterized by chronoamperometry, cyclic voltammetry, the rotating disk electrode technique, X-ray photoelectron spectroscopy and Raman spectroscopy.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Electrooxidative polymerization of phenothiazine derivatives on screen-printed carbon electrode and its application to determine NADH in flow injection analysis system

The electrooxidation polymerization of phenothiazine derivatives, including azure A and toluidine blue 0, has been studied at screen-printed carbon electrodes in neutral phosphate buffer. Both compounds yield strongly adsorbed electroactive polymer with reversible behavior and formal potentials closed to 0.04 V at pH 6.9. The modified electrodes exhibited good stability and electrocatalysis for NADH oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 500 mV lower than that of the bare electrodes. Further, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5-100 muM.

Electropolymerization of azure B on a screen-printed carbon electrode and its application to the determination of NADH in a flow injection analysis system

The electrooxidation polymerization of azure B on screen-printed carbon electrodes in neutral phosphate buffer was studied. The poly(azure B) modified electrodes exhibited excellent electrocatalysis and stability for dihydronicotinamide adenine dinucleotide (NADH) oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 400 mV lower than that at the bare electrodes. Different techniques, including cyclic voltammetry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy have been employed to characterize the poly (azure B) film. Furthermore, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5 muM to 100 muM.