Electrosynthesis and efficient electrocatalytic performance of poly(neutral red)/ordered mesoporous carbon composite

A novel composite film which contains ordered mesoporous carbon (OMC) along with the incorporation of poly(neutral red) (PNR) has been synthesized on glassy carbon electrode by potentiostatic method. This composite film was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV). Two pairs of the redox peaks appear at formal potential E^0′ = +0.045 V (peak I) and E^0′ = −0.49 V (peak II) at the PNR/OMC/GC electrode. And it is found that only the redox waves (peak I) exhibits good electrocatalytic activity towards nicotinamide adenine dinucleotide (NADH) and 2-mercaptoethanol (2-ME). Under a lower operation potential of +0.07 V, amperometry method was used to determine the concentration of NADH and 2-ME, respectively. In pH 7.0, sensors for two molecules under their corresponding optimized conditions were developed with acceptable sensitivity and low detection limits in large determination ranges. In addition, these sensors have good reproducibility and stability.     

Ethanol electrooxidation on platinum particles dispersed on poly(neutral red) film

The conductive polymer poly(neutral red) polymerized on a graphite electrode (PNR/graphite) as a support material was used for catalytic oxidation of ethanol in acidic solution and investigated by electrochemical methods. Pt particles loaded on the surface of PNR/graphite electrode exhibited higher electrocatalytic activity for ethanol oxidation in comparison with Pt particles supported directly on graphite. With the equivalent loading mass of Pt catalyst, the special activity (S _A ) at peak a of the Pt/PNR/graphite electrode polymerized for 10 cycles in 5 × 10⁻⁴ M NR + 0.5 M H₂SO₄ solution is 3,478 A C⁻¹ and about 2.20 times higher than that of the Pt/graphite electrode (1,582 A C⁻¹). The results show that the electrochemical performance of Pt catalyst for ethanol oxidation is improved by the addition of PNR     

Electrosynthesis and electrochemical characterisation of phenazine polymers for application in biosensors

A comparative investigation has been undertaken of the electrosynthesis and electrochemical properties of three different electroactive polymers on carbon film electrode substrates: poly(neutral red) from the phenazine dye neutral red, and poly(methylene green) and poly(methylene blue), from the corresponding phenothiazine dyes. The formation of the radical cation at different potentials and the chemical structures of the monomers both influence the electropolymerisation process of the three polyaromatic dyes. Of the three, poly(neutral red) is shown to have the best adhesion at carbon film electrodes. The influence of the electrolyte and pH on film growth and on electrochemical properties was investigated. The formal potential decreased linearly with increase in pH, in the pH range from 1 to 7 for all three polymers. The modified electrodes were also characterised by electrochemical impedance spectroscopy. The bulk and interfacial characteristics of the two phenothiazine polymers were similar and oxygen-dependent, but different to those of the phenazine polymer, poly(neutral red), which were not significantly influenced by the presence of oxygen in solution. Perspectives for use in electrochemical biosensors are indicated.     

Electrosyntheses of poly(neutral red), a polyaniline derivative

The electrochemical oxidation of neutral red in 0.5 mol dm⁻³ H₂SO₄ solution was carried out by using repeated potential cycling between −0.20 and 1.20 V (versus SCE). The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 4.0. The result from the X-ray photoelectron spectroscopy (XPS) experiment shows that the anions can be doped into the polymer film during the electropolymerization reaction of neutral red. The scanning electron microscopy (SEM) micrograph shows the surface of poly(neutral red) film deposited on the platinum foil is covered with a micro-structured network of mass interwoven fibers with a diameter of 2-4 μm. A straight fiber of the unsystematic micro-fibers is longer than 0.4 mm. The UV-vis spectrum and infrared spectrum (IR) of the polymer are different from those of the monomer.     

Electrosynthesis of poly(neutral red) incorporated with ferrocenesulfonic acid

The electrochemical oxidation of neutral red in 0.5 mol dm⁻³ sulfuric acid and 0.2 mol dm⁻³ ferrocenesulfonic acid solution was carried out using repeated potential cycling between −0.20 and 1.40 V (versus SCE). The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 7.0. The result from the X-ray photoelectron spectroscopy (XPS) experiment shows that the anions can be doped into the polymer film during the electrochemical polymerization reaction of neutral red. The scanning electron microscopy (SEM) micrograph shows that the surface of the resulting polymer film formed on the platinum foil is covered with a compact surface consisting of micro fibers. The visible spectrum and infrared spectrum (IR) of the polymer are different from those of the corresponding monomer. A possible chemical structure of the resulting polymer was also proposed.     

Synthesis and electrochemical capacitance of core-shell poly (3,4-ethylenedioxythiophene)/poly (sodium 4-styrenesulfonate)-modified multiwalled carbon nanotube nanocomposites

A noncovalent method was used to functionalize multiwalled carbon nanotubes with poly (sodium 4-styrene sulfonate). And then, the core-shell poly (3,4-ethylenedioxythiophene)/functionalized multiwalled carbon nanotubes (PEDOT/PSS-CNTs) nanocomposite was successfully realized via in situ polymerization under the hydrothermal condition. In the process, PSS served for not only solubilizing and dispersing CNTs well into an aqueous solution, but also tethering EDOT monomer onto the surface of CNTs to facilitate the formation of a uniform PEDOT coating. Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the resultant PEDOT/PSS-CNTs. In addition, the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) had a specific capacitance (SC) of 198.2 F g⁻¹ at a current density of 0.5 A g⁻¹ and a capacitance degradation of 26.9% after 2000 cycles, much better than those of pristine PEDOT and PEDOT/CNTs (50 wt.% PEDOT). The enhanced electrochemical performance of the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) should be attributed to the high uniform system of the nanocomposite, resulting in the large surface easily contacted by abundant electrolyte ions through the three-dimensional conducting matrix.     

Fabrication and characterisation of novel screen-printed tubular microband electrodes, and their application to the measurement of hydrogen peroxide

A new method of using screen-printed carbon electrodes (SPCEs) incorporating the electrocatalyst cobalt phthalocyanine (CoPC) for the manufacture of tubular microband electrodes for hydrogen peroxide detection is described. Characterisation of these electrodes using potassium ferrocyanide, with cyclic voltammetry, has shown that steady state behaviour is displayed which is indicative of microelectrode behaviour. The current density obtained from the voltammogram was compared to that obtained for a conventional sized CoPC-SPCE, and the values were 5618 and 35.65 μA cm⁻², respectively. Cyclic voltammetry was carried out for the same electrodes, using 7 mM H₂O₂ prepared in phosphate buffer at scan rates between 1 and 50 mV s⁻¹ and no significant increase in current response was observed. The application of these tubular microband CoPC-SPCEs, to the measurement of H₂O₂ using chronoamperometry was investigated. A calibration study was performed and the plot showed a sensitivity value of 252 μA mM⁻¹ cm⁻² and a lower detection limit of 70 μM. We have shown that the chronoamperometric current response could be calculated using a modified equation originally developed for a plain microband electrode. This study provides a platform for using screen-printed carbon electrodes for the fabrication of oxidase based microbiosensors, for the determination of a variety of cellular metabolites.     

Development and characterisation of a novel composite electrode material consisting of poly(3,4-ethylenedioxythiophene) including Au nanoparticles

Composite material consisting of poly(3,4-ethylenedioxythiophene) (PEDOT), including Au nanoparticles encapsulated by N-dodecyl-N,N-dimethyl-3-ammonium-1-propanesulphonate (SB12) is synthesised by constant-current method on ITO glass, in aqueous medium, leading to an electrode coating. The synthesis process is followed by UV-vis spectroelectrochemistry, both in normal-beam and in parallel-beam configurations. Under the same experimental conditions PEDOT is also synthesised by electropolymerisation only in the presence of LiClO₄ supporting electrolyte, as well in solutions also containing SB12. The data relative to the electrosynthesis of the three materials are compared. The composite material based on the conductive polymer matrix including Au nanoparticles has been characterised by SEM, TEM, ICP, Raman and UV-vis spectroscopies. The behaviour of the three different electrode coatings with respect to p-doping process has been studied by conventional electrochemical techniques and by potentiostatic and potentiodynamic UV-vis spectroelectrochemical methods. Conclusions are drawn out about the effect of the presence of the surfactant and of Au nanoparticles on the electrochemical properties of the electrode system.     

Electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with sulfonated thiophenes

Sulfonated thiophenes, sodium 2-(3-thienyloxy)ethanesulfonate (C₆H₇S₂O₄Na) and sodium 6-(3-thienyloxy)hexanesulfonate (C₁₀H₁₅S₂O₄Na), were synthesized and used in the fabrication of ion-selective electrodes (ISEs) sensitive and selective to Ag⁺. The Ag⁺-ISEs were prepared by galvanostatic electropolymerization of 3,4-ethylenedioxythiophene (EDOT) on glassy carbon (GC) electrodes, with either C₆H₇S₂O₄⁻ or C₁₀H₁₅S₂O₄⁻ as the charge compensator (doping ion) for p-doped poly(3,4-ethylenedioxythiophene) (PEDOT). Potentiometric measurements were carried out with these sensors, GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻), to study and compare their sensitivity and selectivity to silver ions. PEDOT(C₆H₇S₂O₄⁻) and PEDOT(C₁₀H₁₅S₂O₄⁻) films were also studied by using other techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance (EQCM) and Fourier transform infrared spectroscopy (FTIR).Results from the potentiometric measurements showed that the difference in length of the alkyl chain of the doping ions C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ has no significant effect on the sensitivity or selectivity of GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻) sensors to Ag⁺. More differences can be seen in the cyclic voltammograms and EIS spectra of the sensors. FTIR spectra confirmed that both C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ act as doping ions in the electrosynthesis of PEDOT-based films and they are not irreversibly immobilized in the polymer backbone.     

Glassy carbon electrodes coated with poly(allylamine hydrochloride), PAH: Characterization studies and application to ion-exchange voltammetry of trace lead(II) at combined PAH/mercury film electrodes

Glassy carbon electrodes coated with adsorbed single layers of the cationic polyelectrolyte poly(allylamine hydrochloride), PAH, were produced by solvent evaporation for subsequent development of PAH modified thin mercury film electrodes (PAH/TMFE). The present work describes the preparation, incorporation features towards lead(II) species, as well as the morphological characterization of PAH coatings of different molar loadings, prepared from polyelectrolyte solutions of different composition. The present PAH films revealed interesting morphologic features, related to the process of solvent evaporation and to the specific structural properties of the PAH polyelectrolyte in the assembling medium.The novel PAH-thin mercury film electrodes, developed for the determination of trace lead(II) as its anionic forms in chloride medium, were found to be stable, sensitive and reproducible. Concentrations in the ppb concentration region could be easily assessed using 20 s accumulation time (detection limit 1.2 ppb, i.e. 6 nM, 3σ) with low relative standard deviations (<2.5%). The sensitivity of the SWASV determination of lead(II) increased 20% compared to the uncoated TMFE. The linearity range reached at least two orders of magnitude. Additionally, the PAH-coated mercury film electrodes presented an improved resistance to fouling by common surfactants.     

Accumulation of Cu(II) cations in poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions and its application in Cu-selective electrodes with PVC based membranes

Electrochemical properties of poly(3,4-ethylenedioxythiophene) doped with hexacyanoferrate(II,III) ions (PEDOT(HCF)) were studied in the presence of Cu²⁺ ions. Voltammetric and EDAX studies revealed retention of hexacyanoferrate anions in the polymer film and accumulation of Cu(II) cations, as well as formation of solid copper hexacyanoferrate near the polymer surface.Accumulation of Cu²⁺ ions was found to be advantageous from the point of view of PEDOT(HCF) applications as a solid contact (ion-to-electron transducer) in all-solid-state Cu²⁺-selective electrodes with solvent polymeric polyvinyl chloride (PVC) based membrane, containing Cu²⁺-selective ionophore. Binding of Cu²⁺ ions in the conducting polymer layer results in analyte ions flux into the transducer phase. Thus, pronounced enhancement of selectivity of the all-solid-state Cu²⁺-selective electrode or lower detection limit of the potentiometric response range was achieved, reaching under optimised conditions 10⁻⁷ M CuSO₄.     

Synthesis, characterization and photoelectrochemical properties of poly(3,4-dioctyloxythiophene)-CdS hybrid electrodes

CdS-poly(3,4-dioctyloxythiophene) (CdS-PDOT) hybrid electrode has been prepared by electrosynthesis of PDOT on Au substrate followed by electrodeposition of Cd and its chemical transformation into CdS. The polymer and semiconductor obtained by this method form hemispherical structures dispersed on the substrate. The synthesized composites were characterized by UV-vis absorption spectra and energy dispersive X-ray spectra (EDS). The AFM images of the electrodes covered with different amounts of each component were correlated with photoactivity of the hybrid electrodes. Photoresponses of Au/PDOT-CdS electrodes under illumination in aqueous solution of Na₂S were also compared with those of CdS without polymer. Enhancement of the photocurrent achieved for some polymer-to-semiconductor ratio is discussed in terms of the hybrid electrode morphology and hole-mediating properties of PDOT. The power conversion efficiency of the device based on CdS-PDOT hybrid electrode was determined from photocurrent-potential behavior of two electrode system, Au/CdS-PDOT/0.1 M Na₂S/Pt with a variable resistance in series in the external circuit.     

Electrocatalytic oxidation of methanol on carbon paste electrode modified by nickel ions dispersed into poly (1,5-diaminonaphthalene) film

Poly (1,5-diaminonaphthalene) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 1.0 M nickel chloride solution. The electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. Also, cyclic voltammetric experiments showed that methanol electrooxidized at the surface of this Ni(II) dispersed polymeric modified carbon paste electrode [Ni/P-1,5-DAN/MCPE]. The mechanism of methanol oxidation changes from diffusion control at low concentration to a catalytic reaction at higher methanol concentration. The effects of both scan rate and methanol concentration on the anodic peak height of the methanol oxidation were discussed.     

聚（3，4-乙撑二氧噻吩）/樟脑磺酸复合材料的合成及其电化学性能

以樟脑磺酸(HCSA)为掺杂剂,FeCl3为氧化剂,通过化学氧化聚合合成了聚(3,4-乙撑二氧噻吩)/樟脑磺酸(PEDOT/HCSA)复合材料;采用FTIR和SEM对其结构和形貌进行了表征;探讨了掺杂剂与单体摩尔比、氧化剂用量和反应时间对产品导电性能的影响;分析了产品的电化学性能。结果表明,当n〔3,4-乙撑二氧噻吩(EDOT)〕:n(樟脑磺酸):n(氯化铁)=2:1:40,反应时间41 h时,复合材料具有良好的导电性能和电化学性能,电导率为10.4 S/cm,经150次充放电老化后比容量可保持在140 F/g左右,是一种潜在的超级电容器电极材料。     

Poly(3,4-ethylenedioxythiophene)/Au-nanoparticles composite as electrode coating suitable for electrocatalytic oxidation

Composite materials consisting of poly(3,4-ethylenedioxythiophene) including Au nanoparticles, encapsulated by citrate anions, have been firmly deposited on an electrode surface through a simple method, taking advantage of the interaction between Au metal and thiophene polymeric backbone. A series of similar electrode coatings, also including different amounts of nanoparticles inside, has been characterised in terms of thickness and surface morphology, through different microscopic techniques. The electrocatalytic properties have been studied with respect to the oxidation of glucose in alkaline media, which is prevented from occurring on the pure organic material.     

Poly(taurine)/MWNT-modified glassy carbon electrodes for the detection of acetaminophen

A novel dye-polymer/CNT, poly(taurine)/MWNT-modified glassy carbon electrode was fabricated. This electrode is based on an electrochemically polymerized taurine layer coated on a MWNT film. The application of this electrode for voltammetric detection of acetaminophen is described. The electroactive surface area of the modified electrode was calculated to be 0.37 cm². Acetaminophen is oxidized at 0.38 V and then reduced at 0.27 V on the modified electrode. The irreversible oxidation process is due to the conversion of acetaminophen into imidogenquinone; the reduction process is ascribed to the reverse electrode reaction. The adsorption-controlled anodic peak current is proportional to the acetaminophen concentration (from 1.0 μM to 0.1 mM) with a detection limit of 0.5 μM. The detection of acetaminophen in drugs was conducted.     

Different steps in the electrosynthesis of poly(3,4-ethylenedioxythiophene) on platinum

The initial stages of poly(3,4-ethylenedioxythiophene) (PEDOTh) film growth on platinum electrodes from TBAClO₄/acetonitrile solution are investigated by means of current-time transient measurements and tapping mode atomic force microscopy. It is shown that, for growth potentials in the range 1.17-1.29 V vs. SCE, the deposition process involves the formation of oligomers in the solution, progressive nucleation of centres of the new phase and three-dimensional growth of a first compact layer followed by a non-uniform distribution of granular-like clusters, whose number and size increase with the synthesis potential and charge. The obtained results reveal that PEDOTh films prepared at distinct potentials but with the same growth charge (Q_g) display similar electroactivities. They also depict that the electrochemical behaviour of the films is a function of the charge used for the synthesis, namely the reduction of tick PEDOTh layers (Q_g > 20 mC cm⁻²) includes more that one step, as a consequence of the formation of a two-layered polymer film.     

Electrical conductivity of poly(3,4-ethylenedioxythiophene):p-toluene sulfonate films hybridized with reduced graphene oxide

Reduced graphene oxide-poly(3,4-ethylenedioxythiophene):p-toluene sulfonate (rGO-PEDOT:PTS) hybrid electrode films were synthesized directly on a substrate by interfacial polymerization between an oxidizing solid layer and liquid droplets of 3,4-ethylenedioxythiophene (EDOT) produced by electrospraying. The EDOT reduced the graphene oxide by donating electrons during its transformation into PEDOT:PTS, and hybrid films consisting of rGO distributed in a matrix of PEDOT:PTS were obtained. These rGO-PEDOT:PTS hybrid films showed excellent electrical conductivities as high as 1,500 S/cm and a sheet resistance of 70 Ω sq^-1. The conductivity values are up to 50% greater than those of films containing conductive PEDOT:PTS alone. These results confirm that highly conductive rGO-PEDOT:PTS hybrid films can potentially be used as organic transparent electrodes.     

Amperometric bienzyme glucose biosensor based on carbon nanotube modified electrode with electropolymerized poly(toluidine blue O) film

The amperometric bienzyme glucose biosensor utilizing horseradish peroxidase (HRP) and glucose oxidase (GOx) immobilized in poly(toluidine blue O) (PTBO) film was constructed on multi-walled carbon nanotube (MWNT) modified glassy carbon electrode. The HRP layer could be used to analyze hydrogen peroxide with toluidine blue O (TBO) mediators, while the bienzyme system (HRP + GOx) could be utilized for glucose determination. Glucose underwent biocatalytic oxidation by GOx in the presence of oxygen to yield H₂O₂ which was further reduced by HRP at the MWNT-modified electrode with TBO mediators. In the absence of oxygen, glucose oxidation proceeded with electron transfer between GOx and the electrode mediated by TBO moieties without H₂O₂ production. The bienzyme electrode offered high sensitivity for amperometric determination of glucose at low potential, displaying Michaelis-Menten kinetics. The bienzyme glucose biosensor displayed linear response from 0.1 to 1.2 mM with a sensitivity of 113 mA M⁻¹ cm⁻² at an applied potential of −0.10 V in air-saturated electrolytes.