Glassy carbon ceramic composite electrodes

A new carbon composite electrode material, based on dispersing glassy carbon (GC) microparticles into methyltrimethoxysilane-derived sol, is described in the present paper. The resulting glassy carbon ceramic composite electrodes (GCCEs) combine the electrochemical properties of GC with the advantages of composite electrodes, and thus offer high electrochemical reactivity, low background current and are easy to prepare, modify and renew. The new material has a low double-layer capacitance and a wide potential window. Scanning electron microscopy (SEM) images indicate significant difference in the structure of GCCE and carbon ceramic composite electrode (CCE). The electrochemical properties and advantages of GCCE should find broad utility in electroanalysis.

Multilayer films of carbon nanotubes and redox polymer on screen-printed carbon electrodes for electrocatalysis of ascorbic acid

Multilayer films containing multiwall carbon nanotubes and redox polymer were successfully fabricated on a screen-printed carbon electrode using layer-by-layer (LBL) assembled method. UV-vis spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and electrochemical method were used to characterize the assembled multilayer films. The multilayer films modified electrodes exhibited good electrocatalytic activity towards the oxidation of ascorbic acid (AA). Compared with the bare electrode, the oxidation peak potential negatively shifted about 350 mV (versus Ag/AgCl). Furthermore, the modified screen-printed carbon electrodes (SPCEs) could be used for the determination of ascorbic acid in real samples.

Electrochemistry of hydroquinone derivatives at metal and iodine-modified metal electrodes

The difference in the electrochemical behavior of hydroquinone and pyrocatechol. at platinum and gold surfaces was analyzed using voltammetry and attenuated total reflection Fourier transform infrared spectroscopy. The results show that the hydroquinone derivatives are adsorbed on a gold surface with vertical orientation, which makes the electron transfer between the bulk species and the electrode surface easier than that in the case of flat adsorption of hydroquinone derivatives that occurs at a platinum electrode. The formation of the vertical conformation and the rapid process of electron transfer were also confirmed by quantum chemistry calculations. In addition, the pre-adsorbed iodine on the electrodes played a key role on the adsorbed configuration and. electron transfer of redox species.

Site-selective self-assembly of MPA-bridged CuHCF multilayers on APTMS-supported gold colloid electrodes

(3-Aminopropyl)trimethoxysilane (APTMS)-supported gold colloid electrode was constructed by virtue of a recently developed solution-based self-assembly strategy. The preparing procedure of 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers on a planar macroelectrode (Bharathi et al. Langmuir 2001, 17, 7468) was copied to the as-prepared colloid electrode. The optical spectra, atomic force microscopy, and electrochemistry demonstrate successful copy of the multilayer system on a macroelectrode to the as-prepared colloid electrode. Remarkably, it was found that multilayer growth is highly selective to the nanoscale sites where gold nanoparticles are immobilized, and multilayer growth does not take place on the sites without nanoparticles. Interestingly, a preliminary electrochemical investigation indicates that electrochemical properties of multilayers systems on the colloid electrode are different from their counterparts on a planar macroelectrode, which might be due to high curvature effects of the gold nanoparticles. This indicates a different motif of multilayers on the colloid electrode from that on a planar macroelectrode.

Bottom-contact organic field-effect transistors having low-dielectric layer under source and drain electrodes

An organic thin-film transistor (OTFT) having a low-dielectric polymer layer between gate insulator and source/drain electrodes is investigated. Copper phthalocyanine (CuPc), a well-known organic semiconductor, is used as an active layer to test performance of the device. Compared with bottom-contact devices, leakage current is reduced by roughly one order of magnitude, and on-state current is enhanced by almost one order of magnitude. The performance of the device is almost the same as that of a top-contact device. The low-dielectric polymer may play two roles to improve OTFT performance. One is that this structure influences electric-field distribution between source/drain electrodes and semiconductor and enhances charge injection. The other is that the polymer influences growth behavior of CuPc thin films and enhances physical connection between source/drain electrodes and semiconductor channel. Advantages of the OTFT having bottom-contact structure make it useful for integrated plastic electronic devices.

Surface-enhanced Raman spectroscopy of microperoxidase-11 on roughed silver electrodes

The conformation of microperoxidase-11 (MP-11) adsorbed on roughened silver electrodes was studied using surface-enhanced Fourier transform Raman spectroscopy. The results demonstrate that MP-11 was initially adsorbed via its polypeptide chain with a alpha-helix conformation, as indicated by the enhancement of the characteristic bands related to the amides I and III. The weak resonance effect of the porphyrin macrocycle in the near IR region contributes to the spectrum of the heme group. The presence of imidazole as the sixth ligand to the heme iron influences the conformation of the polypeptide chain of MP-11 on the electrode surface. Evaporation of solvent water results in an opened conformation of the adsorbed MP-11. which allows the heme group to contact the electrode surface directly.

Carbon ceramic electrodes bulk-modified with nanoparticles of ferrocenebutyrate-intercalated Mg-Al layered double hydroxide

Ferrocenebutyrate-intercalated layered double hydroxide (FcLDH) was prepared by the coprecipitation method and characterized by PXRD, FTIR, TEM and elemental analysis. FcLDH nanoparticles in deionized water were deposited onto the surface of graphite powder to yield graphite powder-supported FcLDH, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing the electroactive ferrocenyl group. Cyclic voltammetric study revealed that peak currents of the FcLDH-modified electrode were diffusion-con trolled in 0.1 mol l(-1) KCl aqueous solution. In addition, the formal potential of the modified electrode is related to the activity of chloride ion with a Nernst slope of 56 mV per decade.

Electrochemiluminescent microoptoprobe with mini-grid working electrode and self-contained sample container

A new electrochemiluminescence (ECL) microoptoprobe with simple structure. small sampling volume and high efficiency was developed. It was constructed by fixing the transparent gold mini-grid on the end surface of the optical fiber, and by surrounding the fiber with the counter- and reference electrodes to form a self-contained three-electrode system. The use of mini-grid electrode increased the surface area and collection efficiency. which resulted in higher ECL signal and better sensitivity. The counter electrode together with one end of the fiber formed a mini-vessel, which eliminated the need of additional container and allowed to perform ECL detection in a very small volume (about 10 mul). The microoptoprobe obtained was characterized with the Ru(bpy)(3)(2-)-tripropylamine system and was applied for the determination of oxalate and chlorpromazine (CPZ). Detection limits (S/N = 3) were 5 x 10(-7) and 1 x 10(-6) mol l(-1) for oxalate and CPZ. respectively. The linear range for oxalate and CPZ extended from 1 x 10(-6) to 1 x 10(-3) mol l(-1), and from 5 x 10(-6) to 5 x 10(-4) mol l(-1). respectively.

Cupric hexacyanoferrate nanoparticle modified carbon ceramic composite electrodes

Graphite powder-supported cupric hexacyanoferrate (CuHCF) nanoparticles were dispersed into methyltrimethoxysilane based gels to produce a conducting carbon ceramic Composite, which was used as electrode material to fabricate surface- renewable CuHCF-modified electrodes. Electrochemical behavior of the CuHCF-modifled carbon ceramic composite electrodes was characterized using cyclic and square-wave voltammetry. Cyclic voltammograms at various scan rates indicated that peak currents were surface-confined at low scan rates. In the presence of glutathione, a clear electrocatalytic response was observed at the CuHCF-modified composite electrodes. In addition, the electrodes exhibited a distinct advantage of reproducible surface-renewal by simple mechanical polishing on emery paper, as well as ease of preparation, and good chemical and mechanical stability in a flowing stream.

Carbon ceramic electrodes modified with sub-micron particles of new methylene blue (NMB) intercalated alpha-zirconium phosphate

New methylene blue-intercalated a-zirconium phosphate (NMBZrP) was synthesized in the presence of n-butylamine and characterized by powder XRD, FTIR, TEM and elemental analysis. Sub-micron particles of NMBZrP in deionized water were apt to deposit onto the surface of graphite powder to yield graphite powder-supported NMBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing new methylene blue. Cyclic voltammetric studies revealed that peak currents of the NMBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled. at high scan rates. In addition, NMBZrP immobilized in a carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution in the pH range from 0.52 to 3.95.

Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Fabrication and electrochemical behaviors of multilayers composed of heteropholyanions and poly(diallyldimethylammonium chloride) on 4-aminothiophenol modified gold electrodes

Multilayer films composed of heteropolyanions (HPAS, SiMo11 VO405-) and cationic polymer poly(diallyldimethylammonium chloride) on 4-aminothiophenol self-assembled-monolayer were fabricated by electrochemical growth. Growth processes of the composite films were characterized by cyclic voltammetry. The results prove the third redox peak of Mo increases more rapidly, otherwise the other Mo redox peaks increase very slowly when the number of layers of heteropolyanions is greater. The peak potentials of composite films shift linearly to negative position with higher pH, which implies that protons are involved in the redox processes of HPA. The investigation of electrocatalytic behaviors of composite films shows a good catalytic activity for the reductions of HNO2 and BrO3-. Catalytic currents increase with increasing number of layers of heteropolyanions, moreover, the catalytic currents have a good linear relationship with the concentrations of BrO3-.

Sol-gel-derived carbon ceramic composite electrodes bulk-modified with 1 : 12-silicomolybdic acid

1:12-Silicomolybdic acid (SiMo12) doped carbon ceramic composite electrodes were fabricated by incorporating SiMo12 and graphite powder in a methyltrimethoxysilane-based gel and characterized by cyclic and square-wave voltammetry, It was demonstrated that the chemically modified electrodes were suitable for electrocatalytic reduction of bromate, The electrodes had the remarkable advantage of surface renewal owing to bulk modification, as web as simple preparation, good mechanical and chemical stability and reproducibility.

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.

Photosensitization of TiO2 nanoparticulate thin film electrodes by CdS nanoparticles

Surface photovoltage spectra (SPS) measurements of TiO2 show that a large surface state density is present on the TiO2 nanoparticles and these surface states can be efficiently decreased by sensitization using US nanoparticles as well as by suitable heat treatment. The photoelectrochemical behavior of the bare TiO2 thin film indicates that the mechanism of photoelectron transport is controlled by the trapping/detrapping properties of surface states within the thin films, The slow photocurrent response upon the illumination can be explained by the trap saturation effect. For a TiO2 nanoparticulate thin film sensitized using US nanoparticles, the slow photocurrent response disappears and the steady-state photocurrent increases drastically, which suggests that photosensitization can decrease the effect of surface states on photocurrent response.