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1.
Polynuclear mixed‐valent films of cobalt oxide and cobalt hexacyanoferrate (CoOCoHCF) have been deposited on electrode surfaces from a solution of Co2+ and Fe(CN)63? ions by repetitive potential cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance measurements demonstrate the steady growth of modified film. The effect of type of monovalent cations as well as acidity of the supporting electrolyte on film growth and redox behavior of resulting film was investigated. In pure supporting electrolyte, electrochemical responses of modified electrode resemble with that of a surface immobilized redox couple. The hybrid film electrodes showed electrocatalytic activity toward oxidation of NADH, hydrazine and hydroxylamine. The feasibility of using our modified electrodes for analytical application was also explored.  相似文献   

2.
The use of a zinc substrate as an electrode and the modification of its surface by means of a thin film of platinum-doped nickel hexacyanoferrate (Pt-NiHCF) were developed. The modification conditions of the zinc surface including the electroless deposition of metallic nickel on the electrode surface from NiCl2 solution, chemical derivatization of the deposited nickel to the NiHCF film in 0.5 M K3[Fe(CN)6] solution, and electrochemical penetration of metallic platinum into the modified film are described. The modified zinc electrodes prepared under optimum conditions show a well-defined redox couple due to the [NiIIFeIII/II(CN)6]1–/2– system. The effects of pH, the alkali metal cation, and the anion of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied in detail. The diffusion coefficients of hydrated alkali metal cations in the film (D), the transfer coefficient (), and the transfer rate constant for the electron (ks) were calculated in the presence of some alkali metal cations. The electrocatalytic activity of the modified electrode for methanol oxidation was demonstrated. The stability of the modified electrode under various experimental conditions was investigated.  相似文献   

3.
Modification of an aluminum electrode by means of a thin film of cobalt hexacyanoferrate (CoHCF) using electroless and electrochemical procedures is described. The modification conditions of the aluminum surface, including the electroless deposition of metallic cobalt on the electrode surface from CoCl2+NaF solution and the chemical derivatization of the deposited cobalt to give a CoHCF film in 0.25 M KCl+0.25 M K3[Fe(CN)6] solution, have been determined. The modified Al electrodes prepared under optimum conditions show one or two well-defined redox couples in phosphate buffer solutions of pH 7.2, depending on the preparation procedure, due to the [CoIIFeIII/II(CN)6]–/2– system. The effect of pH, alkali metal cations, and anions of the supporting electrolyte on the electrochemical characteristics of the modified electrode were studied. Diffusion coefficients of hydrated Na+ in the film, the transfer coefficient, and the transfer rate constant for electrons were determined. The stability of the modified electrodes under various experimental conditions was studied and their high stability in the sodium phosphate buffer solutions was confirmed. Enhanced stability was observed when the modified electrode was scanned in fresh solutions of RuCl3 between 0 and 1 V for at least 20 cycles, due to the formation of mixed hexacyanoferrates of cobalt and ruthenium. Electronic Publication  相似文献   

4.
于浩  郑建斌 《中国化学》2007,25(4):503-509
A copper hexacyanoferrate modified ceramic carbon electrode (CuHCF/CCE) had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V (vs. SCE) in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient (a) and charge transfer rate constant (ks) for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient (D) of hydrazine in solution and the catalytic rate constant (kcat). Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.  相似文献   

5.
An amperometric sensor constructed by mechanical immobilization of nickel hexacyanoferrate onto the paraffin impregnated graphite electrode is reported. The modified electrode exhibits a reversible redox peak, which corresponds to surface-confined Fe(CN)4- 6/Fe(CN)3- 6reaction. Electrocatalytic oxidation of hydrazine is effective on the modified electrode at a significantly reduced overpotential and in a broader pH range. Linear response for hydrazine is in the range 4.0 × 10–4to 4.0 × 10–3M with a correlation coefficient of 0.9963. The detection limit is 9.6 × 10–5M (S/N = 3). The stability and reproducibility of the modified electrode for the determination of hydrazine is evaluated. The proposed method has been applied for the determination of hydrazine in drinking water.  相似文献   

6.
A polynuclear electronically/ionically (redox) conducting mixed-valent inorganic material such as nickel(II) hexacyanoferrate(II,III), NiHCF, was considered for potential application as a redox mediator (charge relay) in dye-sensitized solar cell (DSSC). The NiHCF redox reactions were found fast and reversible not only when the system was studied as thin film exposed to an aqueous supporting electrolyte but also as bulk material (pasted powder) in solid state, i.e., in the absence of contact with external liquid electrolyte phase. Usefulness of NiHCF material was diagnosed using conventional electroanalytical approaches, solid-state voltammetric methodology, as well as the dynamic electrochemical impedance spectroscopy technique that permitted monitoring of impedance spectra under potentiodynamic conditions. The material was utilized in a mixed-valent state, i.e., as a mixture of K4NiII[FeII(CN)6] and K3NiII[FeIII(CN)6] in which iron(II) and iron(III) sites were at the 1:1 ratio. Under such conditions, dynamics of electron-hopping between mixed-valent iron sites was maximized. Our DSSC utilized cis–dithiocyanoatobis(4,4??dicarboxylic acid-2,2??bipyridine) ruthenium(II) dye (N3) adsorbed onto TiO2 semiconductor and NiHCF as redox mediator. Although performance of our DSSC was not optimized in terms of the NiHCF film thickness and morphology, as well as lower photocurrents in comparison to those characteristic of the iodine/iodide based DSSC were obtained, our system yielded readily fairly high open-circuit photovoltages on the level of 800?mV. An important issue was that the formal potential of NiHCF was more positive relative to the potential of the iodide/triiodide couple while being still more negative than that equivalent to the ground state of the N3 dye. Thus, NiHCF mediator was able to regenerate the dye.  相似文献   

7.

A polynuclear electronically/ionically (redox) conducting mixed-valent inorganic material such as nickel(II) hexacyanoferrate(II,III), NiHCF, was considered for potential application as a redox mediator (charge relay) in dye-sensitized solar cell (DSSC). The NiHCF redox reactions were found fast and reversible not only when the system was studied as thin film exposed to an aqueous supporting electrolyte but also as bulk material (pasted powder) in solid state, i.e., in the absence of contact with external liquid electrolyte phase. Usefulness of NiHCF material was diagnosed using conventional electroanalytical approaches, solid-state voltammetric methodology, as well as the dynamic electrochemical impedance spectroscopy technique that permitted monitoring of impedance spectra under potentiodynamic conditions. The material was utilized in a mixed-valent state, i.e., as a mixture of K4NiII[FeII(CN)6] and K3NiII[FeIII(CN)6] in which iron(II) and iron(III) sites were at the 1:1 ratio. Under such conditions, dynamics of electron-hopping between mixed-valent iron sites was maximized. Our DSSC utilized cis–dithiocyanoatobis(4,4′-dicarboxylic acid-2,2′-bipyridine) ruthenium(II) dye (N3) adsorbed onto TiO2 semiconductor and NiHCF as redox mediator. Although performance of our DSSC was not optimized in terms of the NiHCF film thickness and morphology, as well as lower photocurrents in comparison to those characteristic of the iodine/iodide based DSSC were obtained, our system yielded readily fairly high open-circuit photovoltages on the level of 800 mV. An important issue was that the formal potential of NiHCF was more positive relative to the potential of the iodide/triiodide couple while being still more negative than that equivalent to the ground state of the N3 dye. Thus, NiHCF mediator was able to regenerate the dye.

  相似文献   

8.
Silica sol-gel (SG) films with templated pores were deposited on glassy carbon (GC) electrodes by an electrochemically initiated process. Generation-4 poly(amidoamine), PAMAM, dendrimer was included in the tetraethoxysilane precursor to facilitate pore formation. The PAMAM adsorbs to the GC, which blocks SG formation at those sites on the electrode. The pore size was 10?±?5?nm. After removal of the PAMAM, cyclic voltammetry of Fe(CN)6 3? and Ru(NH3)6 3+ at pH?6.2 showed that the residual negative charge on the silica attenuated the current for the former and increased the current for the latter, presumably by electrostatic repulsion and ion-exchange preconcentration, respectively. This premise was supported by repeating the measurements at the isoelectric point. Methylation of the silanol sites was used to eliminate the charge of the SG. At the end-capped SG, the voltammetry of Fe(CN)6 3? and Ru(NH3)6 3+ yielded currents that were independent of pH over the range 2.1 to 7.2. Circumventing the need for the silanization by using (3-glycidyloxypropyl)trimethoxysilane as the sol-gel precursor failed because the oxygen plasma treatment to remove the PAMAM attacked the organically modified sol-gel backbone. The resulting modified electrode mitigated the influence of proteins on the voltammetry of test species and stabilized functionalize nanoparticle catalysts under hydrodynamic conditions.  相似文献   

9.
A novel bimediator amperometric sensor is fabricated for the first time by surface modification of graphite electrode with thionine (TH) and nickel hexacyanoferrate (NiHCF). The electrochemical behavior of the TH/NiHCF bimediator modified electrode was characterized by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The TH/NiHCF bimediator modified electrode exhibited a pair of distinct redox peaks for NiHCF and TH with formal potentials of 0.33 V and −0.27 V vs. SCE at a scan rate of 50 mV s−1 in 0.1 M NaNO3 and 0.1 M NH4NO3 respectively. The electrocatalytic activity of the bimediator modified electrode towards oxidation of gallic acid with NiHCF and reduction of hydrogen peroxide with TH was evaluated and it was observed that the modified electrode showed an electrocatalytic activity towards the oxidation of gallic acid in the concentration range of 4.99 × 10−6–1.20 × 10−3 M with a detection limit of 1.66 × 10−6 M (S/N = 3) and reduction of H2O2 in the concentration range of 1.67 × 10−6–1.11 × 10−3 M with a detection limit of 5.57 × 10−7 M (S/N = 3). The bimediator modified electrode was found to exhibit good stability and reproducibility.  相似文献   

10.
Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)3?6 ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)6 at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)3?6 in a bulk solution was examined in order to understand the transport process of Fe(CN)?36 through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)3?6 within the membrane was found to obey Fick's Law.  相似文献   

11.

Silica sol-gel (SG) films with templated pores were deposited on glassy carbon (GC) electrodes by an electrochemically initiated process. Generation-4 poly(amidoamine), PAMAM, dendrimer was included in the tetraethoxysilane precursor to facilitate pore formation. The PAMAM adsorbs to the GC, which blocks SG formation at those sites on the electrode. The pore size was 10 ± 5 nm. After removal of the PAMAM, cyclic voltammetry of Fe(CN)6 3− and Ru(NH3)6 3+ at pH 6.2 showed that the residual negative charge on the silica attenuated the current for the former and increased the current for the latter, presumably by electrostatic repulsion and ion-exchange preconcentration, respectively. This premise was supported by repeating the measurements at the isoelectric point. Methylation of the silanol sites was used to eliminate the charge of the SG. At the end-capped SG, the voltammetry of Fe(CN)6 3− and Ru(NH3)6 3+ yielded currents that were independent of pH over the range 2.1 to 7.2. Circumventing the need for the silanization by using (3-glycidyloxypropyl)trimethoxysilane as the sol-gel precursor failed because the oxygen plasma treatment to remove the PAMAM attacked the organically modified sol-gel backbone. The resulting modified electrode mitigated the influence of proteins on the voltammetry of test species and stabilized functionalize nanoparticle catalysts under hydrodynamic conditions.

  相似文献   

12.
《Electroanalysis》2003,15(22):1756-1761
Mercaptoundecanoic acid (MUA) and glutathione (GSH) self‐assembled monolayers were prepared on gold‐ wire microelectrode. Cyclic voltammetry was used to investigate the influence of temperature on electrochemical behaviors of Fe(CN)63?/4? and Ru(NH3)63+/2+ at these SAMs modified electrodes in aqueous solution. It is found that temperature shows great influence on electron transfer (ET) and mass transport (MT) for the two SAMs modified electrodes and the influence of temperature depends on the charge properties of the redox couples and terminal groups of SAMs and the structure of the monolayer on gold surface. The temperature can greatly increase MT rate of Fe(CN)63?/4? at both MUA and GSH modified electrodes. However, the increased MT rate doesn't have any effect on the CV's for Fe(CN)63?/4? /MUA system. For Ru(NH3)63+/2+ , temperature can greatly improve the electrochemical reaction in both MUA and GSH modified electrodes, which is ascribed to temperature‐induced diffusion and convection and the electrostatic interaction between Ru(NH3)63+/2+ and negatively charged carboxyl groups on the electrode surface.  相似文献   

13.
采用直接混合法制得平均尺寸小于50 nm的六氰合铁酸钴纳米粒子,元素分析表明其计量学分子式为K0.2Co1.4[Fe(CN)6]•xH2O,红外光谱证明此物质是由铁磁性的CoII1.5[FeIII(CN)6]和反铁磁性的KCoIII[FeII(CN)6]组成,并含有一定量的结晶水。用六氰合铁酸钴纳米粒子修饰的玻碳电极具有良好的稳定性和可逆的循环伏安行为,其电化学特征受溶液中配对阳离子种类和支持电解质浓度的影响。作为电极表面的媒介体,该薄膜对多巴胺的氧化还原具有电催化作用。  相似文献   

14.
We are reporting the highly sensitive determination of hydroxylamine (HA) using 2-mercapto-4-methyl-5-thiazoleacetic acid (TAA) capped fused spherical gold nanoparticles (AuNPs) modified Au electrode. The fused TAA-AuNPs were immobilized on (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film, which was pre-assembled on Au electrode. The immobilization of fused TAA-AuNPs on MPTS sol-gel film was confirmed by UV-vis absorption spectroscopy and atomic force microscopy (AFM). The AFM image showed that the AuNPs retained the fused spherical morphology after immobilized on sol-gel film. The fused TAA-AuNPs on MPTS modified Au electrode were used for the determination of HA in phosphate buffer (PB) solution (pH = 7.2). When compared to bare Au electrode, the fused AuNPs modified electrode not only shifted the oxidation potential of HA towards less positive potential but also enhanced its oxidation peak current. Further, the oxidation of HA was highly stable at fused AuNPs modified electrode. Using amperometric method, determination of 17.5 nM HA was achieved for the first time. Further, the current response of HA increases linearly while increasing its concentration from 17.5 nM to 22 mM and a detection limit was found to be 0.39 nM (S/N = 3). The present modified electrode was also successfully used for the determination of 17.5 nM HA in the presence of 200-fold excess of common interferents such as urea, NO2, NH4+, oxalate, Mn2+, Na+, K+, Mg2+, Ca2+, Ba2+ and Cu2+. The practical application of the present modified electrode was demonstrated by measuring the concentration of HA in ground water samples.  相似文献   

15.
The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10−6 to 1.5×10−4 M (R2=0.9973) and from 1.55×10−4 to 3×10−4 M (R2=0.9983), detection limit=1×10−6 M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.  相似文献   

16.
The surface of a gold (Au) disk electrode was modified with a self‐assembled monomolecular layer of dithiobis(4‐butylamino‐m‐phenylboronic acid) (DTBA‐PBA) to prepare L ‐lactate‐sensitive electrodes. The DTBA‐PBA‐modified electrodes exhibited an attenuated cyclic voltammogram (CV) for the Fe(CN)63? ion in the presence of L ‐lactate, as a result of the formation of phenylboronate ester of L ‐lactate accompanied with the addition of OH? ion to the boron atom. In other words, the negatively charged DTBA‐PBA monolayer blocked the electrode surface from the access of the Fe(CN)63?/4? ions. Thus, the DTBA‐PBA monolayer‐modified Au electrode can be used for determining L ‐lactate on the basis of the change in redox current of Fe(CN)63?/4? ions. The calibration graph useful for determining 1–30 mM L ‐lactate was obtained.  相似文献   

17.
A simple electrochemical procedure to tailor thin polymeric films containing the [FeII(bpy)2(CH3CN)2]2+ and/or [FeII(bpy)3]2+-like cores have been described (bpy=2,2-bipyridine). The procedure is based on the electroreductive precipitation of soluble polymers prepared in situ in CH3CN by mixing Fe3+ ions and a bis bipyridyl ligand, (chiragen: chir). In the resulting [FeII(chir)(CH3CN)2]n2+ films, the two labile S ligands can be easily replaced by a bidentate ligand. This method has been applied with success to design a modified electrode with a supramolecular structure.  相似文献   

18.
《Electroanalysis》2006,18(5):507-512
A coumestan derivative modified carbon paste electrode (CMCPE) was used as a sensitive electrochemical sensor for determination of electrocatalytic of hydrazine and hydroxylamine. The mechanism of electrocatalytic oxidation of both hydrazine and hydroxylamine using CMCPE was investigated by cyclic voltammetry and polarization studies. The kinetic parameters such as the electron transfer coefficient, α, heterogeneous rate constant, k′, and exchange current density, j0, for oxidation of hydrazine and hydroxylamine at the CMCPE surface were determined using cyclic voltammetry. Further more, the linear dynamic range, sensitivity and limit of detection for hydrazine and hydroxylamine detections were evaluated using differential pulse voltammetry.  相似文献   

19.
A platinum (Pt) film coated n-silicon (Pt/n-n+-Si) was modified with nickel(II)-potassium hexacyanoferrate (NiHCF)-graphene sheets (GS) hybrid and used as a photo-electrochemical (PEC) sensor for non-enzyme hydrogen peroxide (H2O2) detection. A NiHCF film was deposited on the surface of GS/Pt/n-n+-Si electrode by chemical method. The structure and composition of the NiHCF film was characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). PEC behavior of the NiHCF-GS/Pt/n-n+-Si electrode was investigated using cyclic voltammetry (CV) under illumination. The modified electrode has been used as PEC sensor for H2O2 detection with a linear range of 2.0 × 10?6–2.9 × 10?3 M and a detection limit of 1.0 × 10?6 M at a signal-to-noise ratio of 3 in a two-electrode cell with a Pt plate as counter electrode. The characteristics of GS layer have been discussed in both the improvement of sensibility and selectivity.  相似文献   

20.
Porous boron-doped diamond (p-BDD) electrodes of high-surface-area have been prepared on vertically aligned carbon nanotube substrates, and their electrochemical performance has demonstrated promising results for application in electroanalysis. The electrochemical features of the p-BDD electrodes were investigated and compared with those of a conventional flat BDD electrode (f-BDD). From cyclic voltammetry studies performed for the electrochemical probes [Fe(CN)6]3? and N,N,N′,N′-tetramethyl-para-phenylenediamine (TMPD), a fast charge transfer was observed at the p-BDD/electrolyte interface. For the [Fe(CN)6]3? redox probe, the heterogeneous electron-transfer rate constant (k 0) value obtained for p-BDD was 10.9 times higher than that obtained using a f-BDD electrode. Moreover, the p-BDD electrodes also gave a smaller peak potential separation, ΔE p, and larger analytical signal magnitude for different biomolecules, such as dopamine (DA), acetaminophen (AC), and epinephrine (EP). These set of results demonstrated that the p-BDD electrode is a suitable candidate for applications in electroanalytical chemistry.  相似文献   

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