Effect of buffer capacity on electrochemical behavior of dopamine and ascorbic acid

It is well known that the electrochemical oxidation of dopamine and ascorbic acid includes the proton and electron transfers at a glassy carbon electrode and their redox potentials are dependent on the pH of solution. When the concentration of the buffer is not enough to neutralize the protons produced by electrochemical oxidation of dopamine and ascorbic acid, two peaks of them can be observed in cyclic voltammograms. The height of the new peak is in proportion to the concentration of proton acceptor including HPO42-, 2,4,6-trimethylpyridine, tris (hydroxymethyl) aminomethane. Moreover, the potential of it is dependent on the type and the concentration of buffer at the same pH of bulk solution. However, this phenomenon cannot be attributed to the interaction between proton acceptor and dopamine or ascorbic acid. So, we think the phenomenon is caused by the acute change of pH at the surface of working electrode. Similar results were also observed in the rotating disk voltammograms. It can be concluded that the electrochemical behavior of some compounds is dependent on the concentration of buffer when this concentration is not enough to neutralize the protons produced in electrochemical oxidation.

Electrochemiluminescence-based DNA detection using guanine oxidation at electrostatic self-assembly of Ru(bpy)(3)(2+)-doped silica nanoparticles on indium tin oxide electrode

A Ru(bpy)(3)(2+)-doped silica nanoparticle-[Ru@Silica] modified indium tin oxide electrode was prepared by simple electrostatic self-assembly technique, and one-electron catalytic oxidation of guanine bases in double-strand and denatured DNA was realized using the electrochemiluminescence detection means.

Assembly of 12-tungstosilicic acid and 4-aminobenzo-15-crown-5 ether based on the electrostatic attraction through bridging of oxonium ions on different substrates

Based on the electrostatic attraction Keggin-type polyoxometalate H4SiW12O40 (SiW12) and small molecule 4-aminobenzo-15-crown-5 ether (4-AB15C5) were alternately deposited on poly (allylamine hydrochloride) (PAH)-derived indium tin oxide (ITO) substrate through a layer-by-layer (LBL) self-assembly, forming a supramolecular multilayer film (film-A). SiW12 was also deposited on a glassy carbon electrode (GCE) derived by 4-AB15C5 via covalent bonding in 0.1 M NaCl aqueous solution and formed a composite monolayer film (film-B). UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy measurements demonstrated that the interactions between SiW12 and 4-AB15C5 in both two film electrodes were the same and caused by the bridging action of oxonium ions. But, the nanostructure in the two film electrodes was different. 4-AB15C5 in film-A was oriented horizontally to ITO substrate, however, that in film-B was oriented vertically to GCE. Namely film-A corresponded to a layer structure, and film-B corresponded to an intercalation structure.

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Controllable synthesis of pd nanocatalysts for direct formic acid fuel cell (DFAFC) application: From pd hollow nanospheres to pd nanoparticles

The controllable synthesis of nanosized carbon-supported Pd catalysts through a surface replacement reaction (SRR) method is reported in this paper. Depending on the synthesis conditions the Pd can be formed on Co nanoparticles surface in hollow nanospheres or nanoparticles structures. Citrate anion acts as a stabilizer for the nanostructures, and protonation of the third carboxyl anion and hence the nanostructure and size of the resulting catalysts are controlled via the pH of the synthesis solution. Pd hollow nanospheres, containing smaller Pd nanoparticles, supported on carbon are formed under the condition of pH 9 reaction solution. Meanwhile, highly dispersed carbon-supported Pd nanoparticles can be formed with higher pH (pH >= 10). All catalysts prepared through the SRR method show enhanced activities for the HCOOH electro-oxidation reaction compared to catalysts reduced by NaBH4.

Large-scale, uniform DNA network on 11-mercaptoundecanoic acid modified gold (111) surface: Atomic force microscopy study

Large-scale, uniform plasmid deoxyribonucleic acid (DNA) network has been successfully constructed on 11-mercaptoundecanoic acid modified gold (111) surface using a self-assembly technique. The effect of DNA concentration on the characteristics of the DNA network was investigated by atomic force microscopy. It was found that the size of meshes and the height of fibers in the DNA network could be controlled by varying the concentration of DNA with a constant time of assembly of 24 h.

Study of carbon-supported Au catalyst as the cathodic catalyst in a direct formic acid fuel cell prepared using a polyvinyl alcohol protection method

In this paper, it is reported for the first time that a carbon-supported Au (Au/C) catalyst for the cathodic catalyst in a direct formic acid fuel cell (DFAFC) was prepared using a polyvinyl alcohol (PVA) protection method. The results indicated that for oxygen reduction, the electrocatalytic activity of the Au/C catalyst prepared with the PVA protection method is much better than that of a Au/C catalyst prepared with the pre-precipitation method. This is due to the small average size and low relative crystallinity of the An particles in the Au/C catalyst prepared by the PVA protection method, compared to that of the Au/C catalyst prepared by the pre-precipitation method, illustrating that the average size and the relative crystallinity of the ALL particles has an effect on the electrocatalytic activity of the Au/C catalyst for oxygen reduction. In addition, because An has no electrocatalytic activity for the oxidation of formic acid, the Au/C catalyst possesses a high formic acid tolerance. After the electrocatalytic activity of the Au/C catalyst for the oxygen reduction is improved, it is suitable to be used as the cathodic catalyst in DFAFC.

Effect of pretreatment of black carbon on electrocatalytic activity of Pt/C catalyst for methanol oxidation

Direct methanol fuel cell (DMFC) has attracted wide attention due to its many advantages. However, its practical application is limited by the low electrocatalytic activity of the anodic Pt/C catalyst usually used for the methanol oxidation. In this paper, in order to increase the electrocatalytic performance of the Pt/C catalyst for the methanol oxidation, the black carbon, usually used as the supporter, was pretreated with CO2, air, HNO3 or H2O2. The cyclic voltarnmetric results indicated that the current densities of the anodic peak of methanol oxidation at the Pt/C catalysts with the black carbon pretreated with CO2,air, HN03, H202 and untreated black carbon were 39, 33, 32, 20 and 18 mA center dot cm(-2), respectively, illustrating that among the above five kinds of the Pt/C catalysts, the Pt/C catalyst with the black carbon pretreated with CO2 shows the best electrocatalytic activity and stability for the methanol oxidation. Its main reason is that the CO2 pretreatment could reduce the content of the oxygen-containing groups on the surface of the black carbon and increase the content of graphite in the black carbon, leading to the low resistance of the black carbon and the increase in the dispersion extent of the Pt particles in the Pt/C catalyst.

Preparation and electrical-magnetic properties of polyaniline doped with ionic ferrocenesulfonic acid

Conducting polyamline with electrical conductivity of 2.34 x 10(-1) S cm(-1) was obtained using ferrocenesulfonic acid as dopant. After the ferrocenesulfonic acid was oxidized with FeCl3, though the electrical conductivity of the doped polyaniline decreased by 1-2 orders of magnitude, the magnetic susceptibility (chi) increased with the increase of the oxidation degree of ferrocenesulfonic acid. EPR spectra showed not only a signal with a g value of around 2, but also a so-called half-field signal with a g value of about 4 even at room temperature. Coexistence of ferromagnetic intrachain interactions and antiferromagnetic interchain interactions in the materials has been suggested.

Electrocatalytic oxidation of catechol at multi-walled carbon nanotubes modified electrode

In 0.05 mol/L phosphate buffer solution (pH 7.0), carbon nanotubes modified electrode exhibits rapid response, strong catalytic activity with high stability toward the electrochemical oxidation of catechol. The electrochemical behavior of catechol on both the multi-walled and single-walled carbon nanotubes modified electrode was investigated. The experimental conditions, such as pH of the solution and scan rate were optimized. The currents (measured by constant potential amperometry) increase linearly with the concentrations of catechol in the range of 2.0 x 10(-5) - 1.2 x 10(-3) mol/L. Moreover, at the multi-walled carbon nanotubes modified electrode the electrochemical responses of catechol and ascorbic acid can be separated clearly.

Fabrication and characterization of hybrid Langmuir-Blodgett films of polyquinoline/stearic acid/rare earth-substituted heteropolymolybdate

Three kinds of hybrid Langmuir-Blodgett films are obtained by the organization of poly(1-hydro-2,2,4-trimethyl)quinoline (PQ), stearic acid(SA) and rare earth-substituted heteropolymolybdates (RE(PMo11)(2), RE = Ce-III, Eu-III, La-III) using the Langmuir-Blodgett technique. They are characterized by pi-A isotherms, absorption spectra, fluorescence spectra, IR and atomic force microscope. The absorption spectra indicate that the molecules of PQ and heteropolymolybdates are incorporated into the LB films. The atomic force microscope reveals that heteropolymolybdates aggregate at the surface of the LB film.

Extraction mechanism of La3+ from hydrochloric acid solution using Cyanex 302

The solvent extraction of La3+ from hydrochloric acid solutions was investigated using his (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302, HL) as an extractant. The effect of equilibrium of aqueous acidity on extraction of La3+ using Cyanex 302 In different diluents was discussed. The effects of extractant concentration and chloride ion on the extraction reaction were also studied. Stoichiometry of the extraction reactions and the nature of metal complexes formed were determined using slope analysis technique and IR measurement.

Effects of a surfactant on the electrocatalytic activity of cobalt hexacyanoferrate modified glassy carbon electrode towards the oxidation of dopamine

The cobalt hexacyanoferrate film (CoHCF) was deposited on the surface of a glassy carbon (GC) electrode with a potential cycling procedure in the presence and absence of the cationic surfactant, cetyl trimethylammonium bromide (CTAB), to form CoHCF modified GC (CoHCF/GC) electrode. It was found that CTAB would affect the growth of the CoHCF film, the electrochemical behavior of the CoHCF film and the electrocatalytic activity of the CoHCF/GC electrode towards the electrochemical oxidation of dopamine (DA). The reasons of the electrochemical behavior of CoHCF/GC electrode influenced by CTAB were investigated using FTIR and scanning electron microscope (SEM) techniques. The apparent rate constant of electrocatalytic oxidation of DA catalyzed by CoHCF was determined using the rotating disk electrode measurements.

Specific determination of As(V) by an acid phosphatase-polyphenol oxidase biosensor

An original amperometric biosensor based on the simultaneous entrapment of acid phosphatase (AcP) and polyphenol oxidase (PPO) into anionic clays (layered double hydroxides) was developed for the specific detection of As(V). The functioning principle of the bienzyme electrode consisted of the successive hydrolysis of phenyl phosphate into phenol by AcP, followed by the oxidation of phenol into o-quinone by PPO. The phenyl phosphate concentration was, thus, monitored by potentiostating the biosensor at -0.2 V vs Ag/AgCl to detect amperometrically the generated quinone. The detection of As(V) was based on its inhibitory effect on AcP activity toward the hydrolysis of phenyl phosphate into phenol. The As(V) can be specifically determined in pH 6.0 acetate buffer without any interferences of As(III) or phosphate, the detection limit being 2 nM or 0.15 ppb after an incubation step for 20 min.