首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Label-free DNA sensors based on porous silicon (PS) substrate were fabricated and electrochemically characterized. p-type silicon wafer was electrochemically anodized in an ethanolic hydrofluoric (HF) solution to construct a PS layer on which polypyrrole (PPy) film was directly electropolymerized. To achieve direct electropolymerization of PPy on PS substrate without pre-deposition of any metallic thin-film underlayer, a low resistivity wafer (0.01–0.02 Ω cm) was used. The rough surface of the PS layer allowed for a strong adsorption of the PPy film. Intrinsic negative charge of the DNA backbone was exploited to electrostatically adsorb 26 base pairs of probe DNA (pDNA) into the PPy film by applying positive bias. The pDNA was designed to hybridize with the target DNA (tDNA) which is the insertion element (Iel) gene of Salmonella enterica serovar Enteritidis. Dependence of peak current (i p ) around 0.2 V vs Ag/AgCl on tDNA concentration and incubation time were shown from the cyclic voltammograms of PS/PPy + pDNA + tDNA substrates in a 0.01 M potassium perchlorate solution. Plot of i p vs incubation time showed a reduction in current density (J) by ca. 29 μA cm−2 every hour. Sensitivity obtained from a plot of i p vs tDNA concentration was −166.6 μA cm−2 μM−1. Scanning electron microscopy (SEM) image of the cross-section of a PS/PPy + pDNA + tDNA multilayered film showed successful direct electropolymerization of PPy for a nano-PS DNA biosensor.  相似文献   

2.
BACKGROUND: Hydrogen peroxide biosensors based on Poly(glycidyl methacrylate‐co‐3‐thienylmethylmethacrylate)/ Polypyrrole [Poly(GMA‐co‐MTM)/PPy] composite film were reported. Poly(GMA‐co‐MTM) including various amounts of GMA and MTM monomers was synthesized via the radical polymerization. Enzyme horseradish peroxidase (HRP) was trapped in Poly(GMA‐co‐MTM)/PPy composites during the electropolymerization reaction between pyrrole and thiophene groups of MTM monomer, and chemically bonded via the epoxy groups of GMA. Analytical parameters of the fabricated electrodes were calculated and are discussed in terms of film electroactivity and mass transfer conditions of the composite films. RESULTS: The amount of electroactive HRP was found to be 1.25, 0.34 and 0.213 µg for the working electrodes of Poly(GMA30%co‐MTM70%)/PPy/HRP, Poly(GMA85%co‐MTM15%)/PPy/HRP and Poly(GMA90%co‐MTM10%)/PPy/HRP, respectively. Optimal response of the fabricated electrodes was obtained at pH 7 and an operational potential of ? 0.35 V. It was observed that effective enzyme immobilization and electroactivity of the composite films could be changed by changing the ratios of GMA and MTM fractions of Poly(GMA‐co‐MTM) based working electrodes. CONCLUSION: The amount of electroactive enzyme increases with increasing MTM content of the final copolymer. High operational stabilities of the biosensors can be attributed to the strong covalent enzyme linkage via the epoxy groups of GMA due to preventing enzyme deterioration and loss. A more convenient microenvironment for mass transfer was provided for the electrodes by higher GMA ratios. It is observed that mass transfer is dominated by the mechanism of electron transfer to obtain effective sensitivity values. This work contributes to discussions clarifying the problems regarding the design parameters of biosensors. Copyright © 2011 Society of Chemical Industry  相似文献   

3.
Highly sensitive glucose oxidase (GOD) electrodes were fabricated on the basis of microstructured polypyrrole (PPy) films. The microstructures of the PPy films had a morphology like cups and were arranged in a density of approximately 4000 units/cm2. GOD was immobilized in microstructured PPy films coated on a Pt or stainless steel (SS; AISI 321) substrate electrode. The GOD/PPy/Pt electrode showed a linear response to glucose concentrations in the range of 0–17 mM at a potential of 0.4 V (vs a saturated calomel electrode). Its sensitivity was measured to be approximately 660 nA/(mM cm2) at 15°C, and the response time (t95%) was approximately 20 s. In comparison, the sensitivity of the GOD/PPy/Pt electrode based on a flat PPy film was only approximately 330 nA/(mM cm2) under the same conditions. The sensitivity of the microstructured GOD/PPy/Pt electrode could be increased to as high as approximately 2400 nA/(mM cm2) at 37°C. The microstructured GOD/PPy/SS electrode had a sensitivity of approximately 550 nA/(mM cm2) and a t95% value of approximately 30 s at 15°C and 0.4 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2550–2554, 2005  相似文献   

4.
We report on the optimum electropolymerization conditions of polypyrrole (PPy) coatings on Mg alloy AZ91D electrodes from aqueous electrolytes of sodium salicylate via cyclic voltammetry (CV). Results show that initial and end potential values during the electrochemical coating procedure play an important role on the adhesion and corrosion performance of PPy films. Corrosion tests of AZ91D electrodes coated with PPy under optimized conditions show a good corrosion performance during 10 days in Na2SO4, without peeling off of these thin films.  相似文献   

5.
The electrosynthesis of polypyrrole (PPy) on copper and brass (Cu–Zn alloy) electrodes was performed by anodic oxidation of pyrrole in a sodium tartrate (C4H4Na2O6 0.2 M) aqueous solution. The tartrate counter-ions slow the dissolution of the working electrode by leading to formation of a passivation layer on its surface, and pyrrole electropolymerization takes place. Strongly adherent and homogeneous polypyrrole films were electrodeposited on Cu and Cu–Zn alloy electrodes using different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. The current densities of electropolymerization on brass are generally greater than those observed on copper. The corrosion behaviour of copper-coated electrodes, electrochemically modified by PPy films, was estimated by DC polarization and weight loss at different current densities in 0.1 M HCl solution. The synthesized polypyrrole films were characterised by several microscopic and spectroscopic techniques such as scanning electron microscopy, X-ray photo electron spectroscopy, Fourier transform infrared and Raman analysis. Galvanostatically deposited PPy films are shown to be an alternative to common black-nickel or black-chromium as a decorative top-coating.  相似文献   

6.
Electropolymerization of 2-aminobiphenyl was carried out on glassy carbon, gold, and platinum electrodes, in aqueous–organic solvent mixtures, using a potentiodynamic technique. The choice of organic solvent strongly influences the film formation. In a mixture of 60% acetonitrile and 40% 1.0M HClO4, stable films were obtained. The poly(2-aminobiphenyl) films were characterized with cyclic voltammetry, where the electrochemical activity of the formed polymer films was investigated in acidic and neutral aqueous solutions containing perchlorates or in potassium ferrocyanide. The prepared films posses a remarkable stability in acidic aqueous solutions and are also stable in some organic solvents. The stability of the polymer films depends on the pH of the solution, and the mechanism of the polymerization process involves deprotonation and head-to-tail coupling of oxidized monomers with its oligomeric radical cations. The kinetics of the electropolymerization process was investigated by determining the charge consumed during the electropolymerization as a function of time at different concentrations of the electrolyte components. The electropolymerization process follows first-order kinetics with respect to the monomer and negative order with respect to HClO4. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

7.
Homogeneous and strongly adherent polypyrrole (PPy) films were electrochemically synthesized on iron electrodes in sodium tartrate (Na2C4O6H4 0.2 M) aqueous solution. This one step pyrrole electropolymerization process has been successfully achieved under different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. During the first stage of the electrochemical process the tartrate counterion slows down the iron dissolution by leading to the formation of a passivation layer on the working electrode surface, and the pyrrole electropolymerization takes place. The electrosynthesized polymer deposit has been characterized by several microscopic and spectroscopic techniques. Any iron traces have been detected by X-ray photoelectron spectroscopy (XPS) on the outer side of the PPy films, which confirms the compactness and the homogeneity of the polymeric coating. Scanning electronic microscopy (SEM) imaging showed uniform and compact PPy coatings with cauliflower-like structure. Infra-red (IR) and Raman spectroscopies proved that the obtained PPy films have the same vibrational properties as those electrodeposited on noble Pt plates.  相似文献   

8.
Nickel oxide/polypyrrole (NiO/PPy) thin films were deposited by a two step process in which the NiO layer was electrodeposited potentiostatically from an aqueous solution of NiCl2·6H2O at pH 7.5 on fluorine doped tin oxide (FTO) coated conducting glass substrates, followed by the deposition of polypyrrole (PPy) thin films by chemical bath deposition (CBD) from pyrrole mixed with ammonium persulfate (APS). The NiO/PPy films were further characterized for their structural, optical, morphological and electrochromic properties. X-ray diffraction study indicates that the films composed of polycrystalline NiO and amorphous PPy. Infrared transmission spectrum reveals chemical bonding between NiO and PPy. Rectangular faceted grains were observed from scanning electron microscopy results. The electrochromic (EC) property of the film was studied using cyclic voltammogram (CV), chronoamperometry (CA) and optical modulation. The NiO/PPy presents superior EC properties than their individual counterparts. The coloration/bleaching kinetics (response time of few ms) and coloration efficiency (358 cm2/C) were found to be improved appreciably. The dramatic improvement in electrochemical stability (from about 500 c/b cycles for PPy to 10,000 c/b cycles for NiO/PPy) was observed. This work therefore demonstrates a cost-effective and simple way of depositing highly efficient, faster and stable NiO/PPy electrodes for EC devices.  相似文献   

9.
A thin Pt layer on fluorine‐doped tin oxide (FTO) glass is commonly used as the counter electrode (CE) for dye‐sensitized solar cells (DSCs). We have investigated thin layers on FTO glass made from spherical polypyrrole (PPy)–poly(styrene sulfonate) (PSS) nanocolloidal particles with and without treatment of CuBr2 and used them as CEs. The colloidal polymer composite (PPy:PSS) was spin‐coated at 4000 rpm, and PPy:PSS multilayer (one, three, five) films were employed as the CEs. Aqueous solutions of CuBr2 (0.5 M and 1 M) were coated onto the multilayer CEs, which increased the efficiency of DSCs. When compared with the untreated PPy:PSS counter electrodes, the CuBr2‐treated PPy:PSS films showed lower charge‐transfer resistance, higher surface roughness, and improved catalytic performance for the reduction of . The enhanced catalytic performance is attributed to the interaction of the superior electrocatalytic activity of PPy:PSS and CuBr2 salt. Under standard AM 1.5 sunlight illumination, the counter electrodes based on a single‐layer PPy:PSS composite with 0.5 M and 1 M CuBr2 salt treatment demonstrated power conversion efficiencies (PCE) of 5.8% and 5.6%, respectively. These values are significantly higher than that of the untreated PPy:PSS CE and are comparable with that of a Pt CE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43772.  相似文献   

10.
This study reports corrosion protection behaviour of various metal cations electrodeposited onto polypyrrole (PPy) coated copper (Cu) electrode. Before electropolymerization of pyrrole, the Cu electrode was passivated in 0.1 M oxalic acid via cyclic voltammetry method. After the coating process, metal cation electrodeposition onto PPy coating was carried out in 10−2 M CuCl2, ZnCl2, FeCl2 and NiCl2 solutions. Corrosion behaviour of uncoated, PPy and PPy|metal coated Cu electrodes was studied in 0.1 M H2SO4 solution by using potentiodynamic polarization, chronoamperometric and impedance spectroscopic measurements. Surface morphologies were examined by scanning electron microscope (SEM). All the electrochemical measurements were in good agreement showing that metal electrodeposited PPy coated Cu electrodes have a higher corrosion resistance. Furthermore, SEM results show that while all the samples have a homogeneous distribution of metal cations, zinc and nickel have a much better homogeneous distribution compared to copper and iron. It was found that the best corrosion protection is provided by PPy|Zn and PPy|Ni coatings and there is a significant increase in their polarization resistance with increasing amounts of electrodeposited cations.  相似文献   

11.
Functionalized polypyrrole (PPy) films were prepared by incorporation of anthraquinonedisulphonate (AQDS) as doping anion during the electropolymerization of pyrrole (Py) monomer at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the PPy-bound AQDS modified electrode and cathodic reduction of oxygen on the resulting polymer film were studied. An obvious surface redox reaction corresponding to AQ/H2AQ was observed and the dependence of this reaction on the solution pH was also illustrated. The electrocatalytic ability of the PPy-bound AQDS modified electrode was demonstrated by the electroreduction of oxygen at the optimized pH of 6.3 in a phosphate buffer. The reduced AQDS (H2AQ) is responsible for the extraordinary catalytic activity to the oxygen reduction reaction. The PPy layers not only act as an electron mediator, but also facilitate the stability of the modified electrode. It was found that the catalytic reaction occurred in the presence of the bound AQDS and O2 is in agreement with an electrochemical–chemical (EC) mechanism. The kinetic parameters of oxygen reduction were determined using Koutecky–Levich equation and Tafel polarization technique.  相似文献   

12.
In this contribution, 2‐(9H‐carbazol‐9‐yl) ethyl methacrylate (CzEMA) monomer was chemically synthesized. The monomer characterization was performed by FT‐IR, 1H‐NMR, 13C‐NMR, and melting point analysis. The electropolymerization of CzEMA was studied onto carbon fiber microelectrodes (CFMEs) as an active electrode material in 0.1M sodium perchlorate (NaClO4)/acetonitrile (ACN) solution. The electropolymerization experiments were done from 1 mM to 10 mM. The detailed characterization of the resulting electrocoated Poly (CzEMA)/CFME thin films was studied by various techniques, i.e., cyclic voltammetry (CV), Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The effects of initial monomer concentrations (1, 3, 5, and 10 mM) during the preparation of modified electrodes were examined by EIS. Capacitive behaviors of modified CFMEs were defined via Nyquist, Bode‐magnitude, and Bode‐phase plots. Variation of capacitance values by initial monomer concentration and specific capacitance values are presented. The highest specific capacitance value electrocoated polymer thin film by CV method in the initial monomer concentration of 5 mM with a charge of 52.74 mC was obtained about 424.1 μF cm?2. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

13.
This paper describes the study of the preparation of Ti/Ti1-xCexO2 electrodes using the Pechini method and their application for the electroreduction of nitrobenzene in aqueous acid medium. The electrodes were studied using X-ray diffraction, and scanning electron microscopy and it was found that the electrocatalytic properties are influenced by the microstructure and morphology of the electrodes. All doped electrodes presented an enhanced performance for nitrobenzene electroreduction when compared to pure TiO2. The Ti0.995Ce0.005O2 electrode presented the best performance, with an increase of 58% in the aniline yield under galvanostatic electrolysis conditions.  相似文献   

14.
To improve the protection against the corrosion of AZ91D magnesium alloy provided by conducting polypyrrole (PPy) films, optimization of the electrochemical synthesis of the PPy film was investigated. The bi-layered PPy film was prepared under constant current control, first in a sodium tartrate solution containing molybdate and second in a sodium dodecylsulfate (DS) solution (after the AZ91D alloy was covered by zinc electroplating). Corrosion testing of the zinc-coated AZ91D alloy covered with the PPy film was performed in 3.5% NaCl solution. The more protective PPy film doped with tartrate ions (PPy-Tart film) was formed by the lower current density (CD). Doping of molybdate ions (MoO42−) into the PPy-Tart film significantly improved its corrosion protection properties. When the PPy-Tart-MoO4 layer was covered by an outer PPy layer doped with DS ions, the corrosion protection was further improved. The imposition of ultrasonic waves during the electropolymerization of the inner PPy-Tart-MoO4 layer was effective in the improvement of corrosion protection. The bi-layered PPy-Tart-MoO4/PPy-DS film prepared under ultrasonic irradiation maintained the zinc-coated AZ91D alloy in the passive state during the corrosion test in NaCl solution for 221 h, during which no corrosion products appeared.  相似文献   

15.
Polyfuran films doped with perchlorate anions (PFu/ClO4) were studied by scanning and transmission electron microscopies under different synthesis conditions. However, an electropolymerization overpotential equal to at least 2.1 V was needed to obtain stable PFu/ClO4 films. In the synthesis conditions analysed, the film growth face presented an ordered nodular structure oriented 45 ° with respect to the lengthwise axis of the electrode. The nodule size and film rugosity were affected by the ratios between furan and NaClO4 concentrations. When the furan concentration was double that of perchlorate, the films were less rough and more homogeneous. © 2000 Society of Chemical Industry  相似文献   

16.
We propose a modified kinetic equation for the galvanostatic electropolymerization of pyrrole based on equal rates of monomer disappearance and its galvanostatic electropolymerization associated with applied current (I). The equation is distinguished by a zero‐order kinetic plot and takes into account the effects of the pyrrole initial concentration ([M]0) and current efficiency (η). We propose a mechanism for obtaining a η of less than 100% and increasing η with increasing [M]0 and I on the basis of the diffusion of radical cations (M?+) from the anode surface to the bulk solution after the electroreduction of M?+ to monomer molecules at the cathode. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1167–1169, 2005  相似文献   

17.
The two-step and one-step electrosynthesis processes of polypyrrole (PPy) films on the zinc substrate are described. The two-step process includes (i) the zinc surface pretreatment with hexacyanoferrate ion in the aqueous medium in order to form a zinc hexacyanoferrate (ZnHCF) film non-blocking passive layer on the surface and with the view to prevent its reactivity and (ii) electropolymerization of pyrrole on the ZnHCF|Zn-modified electrode in aqueous pyrrole solution. In this context, both the non-electrolytic and electrolytic procedures were adapted, and the effect of some experimental conditions such as supporting electrolyte, pH and temperature of the solution at the zinc surface pretreatment step as well as pyrrole concentration and electrochemical techniques at the polymerization step was investigated. By optimizing the experimental conditions in both steps, we have obtained a homogeneous and strongly adherent PPy films on the zinc substrate.The one-step process is based on the use of an aqueous medium containing Fe(CN)64− and pyrrole. The ferrocyanide ion passivates the substrate by formation of ZnHCF film during the electropolymerization process of pyrrole and therefore makes it possible to obtain strongly adherent PPy films, with controlled thickness, either by cyclic voltammetry or by electrolysis at constant current or constant potential without any previously treatment of the zinc electrode surface. The polypyrrole films deposited on the zinc electrode were characterized by cyclic voltammetry and scanning electron microscopic (SEM) measurement.  相似文献   

18.
BACKGROUND: Newly synthesized composite films of P(glycidyl methacrylate85co‐vinylferrocene15)/Poly(glutaraldehyde)/ Polypyrrole [P(GMA85co‐VFc15)/PGA/PPy] and Poly(3‐methylthienyl methacrylate85co‐vinylferrocene15)/Polypyrrole [P (MTM85co‐VFc15)/PPy] were used as matrices for tyrosinase based working electrodes. Direct covalent attachment of enzyme was carried out via the pendant epoxy groups of P(GMA85co‐VFc15) film, and the entrapment of enzyme was achieved for electrode containing P(MTM85co‐VFc15) film via electropolymerization of pyrrole in the presence of enzyme. The aim of the study is amperometric determination of various phenolics and investigation of the effect of interfacial interactions between enzyme and matrices on biosensor response. RESULTS: The lowest detection limit and the highest sensitivity for a P(GMA85co‐VFc15) based working electrode was found to be 0.113 µmol L?1 for 4‐methoxyphenol, 40 nA (µmol L?1)?1 for pyrocatechol, respectively. Results showed that sensitivities were at least 8500–55000 times higher than the results in previous P(GMA‐co‐VFc) related studies. CONCLUSION: Facilitated electron transfer was achieved by means of mediator incorporated in conductive composites of VFc based redox copolymers. The effect was greater when enzyme was covalently bonded via epoxy groups due to the proximity of enzyme, mediator and electrode surface. Results showed that a multifunctional surface was provided on electrodes since the suggested copolymers could mediate an electrochemical reaction, and the multifunctional surface was capable of coating with conductive PPy. Copyright © 2011 Society of Chemical Industry  相似文献   

19.
Thin films of WOx and Pt on WOx were evaporated onto the microporous layer of a gas diffusion layer (GDL) and served as model electrodes in the polymer electrolyte fuel cell (PEFC) as well as in liquid electrolyte measurements. In order to study the effects of introducing WOx in PEFC electrodes, precise amounts of WOx (films ranging from 0 to 40 nm) with or without a top layer of Pt (3 nm) were prepared. The structure of the thin-film model electrodes was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy prior to the electrochemical investigations. The electrodes were analyzed by cyclic voltammetry and the electrocatalytic activity for hydrogen oxidation reaction (HOR) and CO oxidation was examined. The impact of Nafion in the electrode structure was examined by comparing samples with and without Nafion solution sprayed onto the electrode. Fuel cell measurements showed an increased amount of hydrogen tungsten bronzes formed for increasing WOx thicknesses and that Pt affected the intercalation/deintercalation process, but not the total amount of bronzes. The oxidation of pre-adsorbed CO was shifted to lower potentials for WOx containing electrodes, suggesting that Pt-WOx is a more CO-tolerant catalyst than Pt. For the HOR, Pt on thicker films of WOx showed an increased limiting current, most likely originating from the increased electrochemically active surface area due to proton conductivity and hydrogen permeability in the WOx film. From measurements in liquid electrolyte it was seen that the system behaved very differently compared to the fuel cell measurements. This exemplifies the large differences between the liquid electrolyte and fuel cell systems. The thin-film model electrodes are shown to be a very useful tool to study the effects of introducing new materials in the PEFC catalysts. The fact that a variety of different measurements can be performed with the same electrode structure is a particular strength.  相似文献   

20.
The influence of electrolyte and deposition potential on polyfurane doped/undoped electrogenerated films was analyzed by potentiodynamic profiles and current–time transients. The films were formed on platinum electrodes from the monomer and tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, or tetraethylammonium perchlorate in acetonitrile. Results were also discussed with the aid of X‐ray photoelectron spectroscopy (XPS), electron probe microanalysis (EPMA), and primarily by scanning electron microscopy (SEM). It was shown that there is some oxygen contamination not only after ClO4 doping. However, it was shown by XPS and EPMA that C? O? C bonds are present in the films, which confirmed that there was no destruction of the furan ring during electropolymerization. SEM study showed film morphology evolution with monomer concentration, and with the electrolyte or the dopant used. The undoping effect was also visualized, showing that doped polyfuran was more homogeneous than the respective undoped deposits. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1346–1354, 2004  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号