共查询到20条相似文献,搜索用时 31 毫秒
1.
D. Becker 《Electrochimica acta》2003,49(1):29-39
Reversible charge transfer on boron doped diamond (BDD) electrodes was studied using cyclic voltammetry and electrochemical impedance spectroscopy. Polycrystalline diamond films of 5 μm thickness with 200 and 3000 ppm boron content were prepared by chemical vapour deposition on niobium substrate. The samples were mounted in a Teflon holder and used as rotating disk electrodes (RDE) with rotation frequencies between 0 and 4000 rpm. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na2SO4 + 5 mM K3[Fe(CN)6]/K4[Fe(CN)6] and 0.1 M KCl + 5 mM [Ru(NH3)6]Cl2/[Ru(NH3)6]Cl3. The electrochemical redox behaviour of the BDD electrodes was found to differ significantly from that of an active Pt electrode. The deviations are indicated by a large peak potential difference and a shift of the peak potentials in cyclic voltammograms with increasing sweep rate. At rotating electrodes lower limiting current densities are found and the impedance diagrams exhibit an additional capacitive impedance element at high frequencies. The results are described quantitatively by an impedance model which is based on partial blocking of the diamond surface. 相似文献
2.
Saurav K. Guin 《Electrochimica acta》2010,55(28):8402-8409
Porous-polyaniline coated Pt electrode (PANI/Pt) was electro-synthesized potentiodynamically in 0.1 M aniline + 0.5 M H2SO4 and morphologically characterized by scanning electron microscopy (SEM). Nature of predominant Fe-species in HCl and H2SO4 was checked by UV-vis spectrophotometry. Electrocatalysis of Fe(III)/Fe(II) reaction was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for three different solution compositions viz. (i) FeCl3/FeCl2 in 1 M HCl, (ii) FeCl3/FeCl2 in 0.5 M H2SO4 and (iii) Fe2(SO4)3/FeSO4 in 0.5 M H2SO4. For different thicknesses of PANI, the peak current increased irrespective of the nature of the Fe-species, but the polarity of the charge on the Fe-species showed great influence on reversibility of electrocatalysis by PANI/Pt. The Donnan interaction of the polyaniline modified electrode for the three compositions was investigated with respect to [Fe(CN)6]3−/H2[Fe(CN)6]2− which are believed to be the predominant species present in K3[Fe(CN)6]/K4[Fe(CN)6] solution in 0.5 M H2SO4. The electrocatalytic performance of PANI/Pt for Fe(III)/Fe(II) redox reaction was found superior in HCl compared to that in H2SO4. 相似文献
3.
Chengguo Hu 《Electrochimica acta》2004,49(3):405-412
A cetyltrimethyl ammonium bromide modified carbon paste electrode (CTAB/CPE) was developed in this work based on the surface modification method. The improved electrochemical response of K4Fe(CN)6 at this electrode indicated that CTAB could change the surface property of carbon paste electrodes (CPEs), which was demonstrated by the electrochemical impedance spectroscopy (EIS). In 0.1 mM [Fe(CN)6]3−/4−, a low exchange current (i0) of 2.72×10−7 A at bare CPE was observed while that at CTAB/CPE was 6.79×10−5 A. The effect of CTAB concentration on the electrode quality revealed that CTAB formed a compact monolayer on the electrode surface with high density of positive charges directed outside the electrode. This electrode showed strong accumulation ability toward Fe(CN)64− and can also accumulate Co(phen)32+ by the adsorption of the organic ligands in the hydrophobic area of the monolayer. The electrode was applied to the immobilization of DNA, which was characterized by the isotherm adsorption of Co(phen)32+. 相似文献
4.
A glassy carbon (GC) electrode surface was modified with a cadmium pentacyanonitrosylferrate (CdPCNF) film as a novel electrode material. The modification procedure of the GC surface includes two consecutive procedures: (i) the electrodeposition of metallic cadmium on the GC electrode surface from a CdCl2 solution and (ii) the chemical transformation of the deposited cadmium to the CdPCNF films in 0.05 M Na2[Fe(CN)5NO] + 0.5 M KNO3 solution. The modified GC electrode showed a well-defined redox couple due to [CdIIFeIII/II(CN)5NO]0/−1 system. The effects of supporting electrolytes and solution pH were studied on the electrochemical behavior of the modified electrode. The diffusion coefficients of alkali-metal cations in the film (D), the transfer coefficient (α) and the charge transfer rate constant at the modifying film | electrode interface (ks), were calculated in the presence of various alkali-metal cations. The stability of the modified electrode was investigated under various experimental conditions. 相似文献
5.
The electrosynthesis of polyaniline on the bare aluminum and pre-treated aluminum surface achieved in aqueous H2PtCl6 solution saturated with NaF for few seconds is described. The effect of some factors such as pre-treatment time, aniline and sulfuric acid concentrations on the electropolymerization process was investigated and optimum conditions were obtained. The stability of polyaniline film on the pre-treated aluminum electrode (Al-Pt) was studied as function of the potential imposed on the electrode. For applied electrode potentials of 0.1-0.7 V, the first-order degradation rate constant, k, of polyaniline film varies between 1 × 10−6 and 2 × 10−5 s−1, and a relatively low slope (i.e. 2.1) was obtained for the plot of log k versus E. The coatings were characterized by scanning electron microscopy (SEM), and cyclic voltammetric behavior of the polyaniline-deposited Al electrode (Al/PANI) and polyaniline-deposited Al-Pt electrode (Al-Pt/PANI) in 0.1 H2SO4 solutions is described. The electrocatalytic activity of the Al-Pt/PANI electrode against para-benzoquinone/hydroquinone (Q/H2Q) and Fe(CN)63−/Fe(CN)64− redox systems was investigated and the obtained results are compared with those obtained on Al/PANI and bulk Pt electrodes. 相似文献
6.
A novel electrode material was obtained at an aluminum electrode (Al) by a simple electroless method including two consecutive procedures: (i) the electroless deposition of metallic palladium on the Al electrode surface from PdCl2 + 25% ammonia solution and (ii) the chemical transformation of deposited palladium to the palladium hexacyanoferrate (PdHCF) films in a solution containing 0.5 M K3[Fe(CN)6]. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of dopamine (DA). The effect of solution pH on the voltammetric response of DA has been investigated. A linear calibration graph was obtained over the DA concentration range 2-51 mM. The rate constant k and transfer coefficient α for the catalytic reaction and the diffusion coefficient of DA in the solution D, were found to be 4.67 × 102 M−1 s−1, 0.63 and 2.5 × 10−6 cm2 s−1, respectively. The interference of ascorbic acid was investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level stability during electrochemical experiments, making it particularly suitable for the analytical purposes. 相似文献
7.
Poly(o-aminophenol) (POAP) was formed by successive cyclic voltammetry in monomer solution in the presence of sodium dodecyl sulfate (SDS) on the surface of a carbon paste electrode. The electrochemical behavior of the SDS-POAP carbon paste electrode has been investigated by cyclic voltammetry in 0.5 M HClO4 and 5 mM K4[Fe(CN)6]/0.1 M KCl solutions as the supporting electrolyte and model system, respectively. Ni(II) ions were incorporated into the electrode by immersion of the polymeric modified electrode having amine groups in 0.1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode. A good redox behavior of the Ni(III)/Ni(II) couple at the surface of electrode can be observed. The electrocatalytic oxidations of methanol and ethylene glycol (EG) at the surface of the Ni/SDS-POAP electrode were studied in a 0.1 M NaOH solution. Compared to bare carbon paste and POAP-modified carbon paste electrodes, the SDS-POAP electrode significantly enhanced the catalytic efficiency of Ni ions for methanol oxidation. Finally, using a chronoamperometric method, the catalytic rate constants (k) for methanol and ethylene glycol were found to be 2.04 × 105 and 1.05 × 107 cm3 mol−1 s−1, respectively. 相似文献
8.
Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H2O2, and electrocatalytically oxidation active for S2O42− through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S4O62−, S2O42−, and SO32−, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method. 相似文献
9.
Mohamed A. Ghanem Richard G. Compton Elefteria Psillakis Frank Marken 《Electrochimica acta》2007,53(3):1092-1099
The electrochemical oxidation of phenolic compounds in aqueous media is known to be affected by the formation of electro-polymerized organic layers which lead to partial or complete electrode blocking. In this study the effect of high intensity microwave radiation applied locally at the electrode surface is investigated for the oxidation of phenol and triclosan in alkaline solution at a 500 μm diameter glassy carbon or at a 500 μm × 500 μm boron-doped diamond electrode. The temperature at the electrode surface and mass transport enhancement are determined by calibration with the Fe(CN)63−/4− redox system in aqueous 0.3 M NaOH and 0.2 NaCl (pH 12) solution. The calibration shows that strong thermal and mass transport effects occur at both glassy carbon and boron-doped diamond electrodes. The average electrode temperature reaches up to 390 K and mass transport enhancements of more than 20-fold are possible. For the phenol electro-oxidation at glassy carbon electrodes and at a concentration below 2 mM a multi-electron oxidation (ca. 4 electrons) occurs in the presence of microwave radiation. For the electro-oxidation of the more hydrophobic triclosan only the one-electron oxidation occurs. Although currents are enhanced in presence of microwave radiation, rapid blocking of the electrode surface in particular at high phenol concentrations still occurs. 相似文献
10.
Glassy carbon electrode modified with Nafion-Au colloids for clenbuterol electroanalysis 总被引:1,自引:0,他引:1
Stable Nafion-Au colloids were immobilized on a glassy carbon electrode (GCE) for detection of β-agonist clenbuterol by electroanalysis. The Au colloids were prepared by a one-step electrodeposition onto GCE, with obvious electrocatalytic activity present. The negatively charged Nafion film was an efficient barrier to negatively charged interfering compounds, resulting in accumulation of positively charged clenbuterol at the Nafion film. The electrochemical characters of the electrode during various modified steps in a redox probe system of K4[Fe(CN)6]/K3[Fe(CN)6] were confirmed by cyclic voltammetry (CV) and AC-impedance. In Britton-Robinson (B-R) buffer solution (pH = 2.0) and the potential range of −0.2 to 1.2 V, the Nafion-Au colloid modified electrode, compared to a bare GCE, exhibits obvious electrocatalytic activity towards the redox of clenbuterol by greatly enhancing the peak current with a linear calibration curve from 8.0 × 10−7 to 1.0 × 10−5 mol/L and a detection limit of (1.0 × 10−7 mol/L) (R = 0.996). The modified electrode shows high sensitivity, selectivity and reproducibility. The recovery for detecting clenbuterol (∼10−6 mol/L) in human serum is up to 98.19%. 相似文献
11.
Electrochemical behaviour of sandwich-type composite electrodes of polypyrrole (PPy) and CoFe2O4 nanoparticles (Ox) were investigated in an aqueous solution of 0.5 M K2SO4 and 5mM KOH at 25 °C using electrochemical impedance (EI), cyclic voltammetry (CV) and Tafel polarization techniques. EI and CV studies indicated that the incorporation of oxide nanoparticles influenced the charge transfer and transport behaviours of the polymer matrix greatly. The bulk electrical resistances of pure polymer (4.5 ± 1.7 Ω) as well as composite (2.7 ± 0.8 Ω) electrodes were practically constant in the potential region, +0.1 to −0.7 V. The latter electrode showed a good electrocatalytic activity towards the oxygen reduction reaction (ORR). 相似文献
12.
Ivar Kruusenberg 《Carbon》2009,47(3):651-280
The pH-dependence of oxygen electroreduction has been investigated on multi-walled carbon nanotube (MWCNT) modified glassy carbon (GC) electrodes. Various surfactants were used in the electrode modification: dihexadecyl hydrogen phosphate, cetyltrimethylammonium bromide, sodium dodecyl sulfate and Triton X-100. Electrochemical experiments were carried out in 0.5 M H2SO4 solution, acetate buffer (pH 5), phosphate buffers (pH 6, 7 and 8), borate buffer (pH 10), 0.01 M KOH, 0.1 M KOH and in 1 M KOH solution, using the rotating disk electrode (RDE) method. The oxygen reduction behaviour of MWCNT-modified GC electrodes at different pHs was compared. The RDE results revealed that the half-wave potential (E1/2) of oxygen reduction was higher in solutions of high pH. At lower pHs (pH < 10) the value of E1/2 did not essentially depend on the solution pH. A comparison with previous studies on bare GC showed that the pH-dependence of the half-wave potential of oxygen reduction on MWCNT-modified GC electrodes follows a similar trend to that observed for bare GC. 相似文献
13.
Hung-Wei Chu 《Electrochimica acta》2008,53(6):2862-2869
Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H2SO4 solution containing Zn(NO3)2, RuCl3 and K3[Fe(CN)6] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of RuII/III redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and l-cysteine, and reduction of S2O82− and SO52− as well as IO3− using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques. 相似文献
14.
The surface of an aluminum (Al) electrode was modified with a thin film of nickel hexacyanoruthenate (NiHCR) as a novel electrode material. The modification procedure of Al surface, includes two consecutive procedures: (i) the electroless deposition of metallic nickel on the Al electrode surface from NiCl2 solution, and (ii) the chemical transformation of deposited nickel to nickel hexacyanoruthenate films in solution of 20 mM K3[Ru(CN)6] + 0.5 M KNO3. Cyclic voltammogram of the modified Al electrode showed a well-defined redox reaction due to [NiIIRuIII/II(CN)6]1−/2− system. The effects of different supporting electrolytes and solution pH were studied on the electrochemical characteristics of the modified electrode. The diffusion coefficients of K+ and Na+ cations in the film (D), the transfer coefficient (α), and the charge transfer rate constant at the modifying film/electrode interface (ks), were calculated in the presence of both K+ and Na+ cations. The stability of the modified electrode was investigated under various experimental conditions. 相似文献
15.
This paper describes a simple and rapid photocatalytic pretreatment procedure that removes contaminants from glassy carbon (GC) surfaces. The effectiveness of TiO2 mediated photocatalytic pretreatment procedure was compared to commonly used alumina polishing procedure. Cyclic voltammetric and chronocoulometric measurements were carried out to assess the changes in electrode reactivity by using four redox systems. Electrochemical measurements obtained on photocatalytically treated GC electrodes showed a more active surface relative to polished GC. In cyclic voltammograms of epinephrine, Fe(CN)63−/4− and ferrocene redox systems, higher oxidation and reduction currents were observed. The heterogeneous electron transfer rate constants (ko) were calculated for Fe(CN)63−/4− and ferrocene which were greater for photocatalytic pretreatment. Chronocoulometry was performed in order to find the amount of adsorbed methylene blue onto the electrode and was calculated as 0.34 pmol cm−2 for photocatalytically pretreated GC. The proposed photocatalytic GC electrode cleansing and activating pretreatment procedure was more effective than classical alumina polishing. 相似文献
16.
A novel cholesterol biosensor based on capacitive detection has been developed using molecularly imprinted polymers. The sensitive layer was prepared by electropolymerization of 2-mercaptobenzimidazole (2-MBI) on a gold electrode in the presence of cholesterol as a template. Cyclic voltammetry and capacitive measurements were used to monitor the process of electropolymerization. Surface uncovered areas were plugged with 1-dodecanethiol to make the layer dense, and the insulating properties of the layer were studied in the presence of K3Fe(CN)6/K4Fe(CN)6 redox couples and also by the use of AC impedance measurements. The template molecules and the non-bound thiol were removed from the modified electrode surface by washing with an alkaline solution of ethanol. The sensor's linear response range was between 5 and 30 μM, with a detection limit of 0.42 μM. The proposed molecularly imprinted polymer capacitive (MIPC) sensor exhibited good selectivity for cholesterol. The reproducibility and repeatability of the MIPC senor were all found to be satisfactory. The results from sample analysis confirmed the applicability of the MIPC sensor to quantitative analysis. 相似文献
17.
The sol-gel technique was used to construct nickel pentacyanonitrosylferrate (NiPCNF) modified composite ceramic carbon electrodes (CCEs). This involves two steps: forming a CCE containing Ni powder and then immersing the electrode into a sodium pentacyanonitrosyl-ferrate solution (electroless deposition). The cyclic voltammograms of the resulting surface modified CCE under optimum conditions show a well-defined redox couple due to the [NiIIFeIII/II(CN)5NO]0/−1 system. The electrochemical properties and stability of the modified electrode were investigated by cyclic voltammetry. The apparent electron transfer rate constant (ks) and transfer coefficient (α) were determined by cyclic voltammetry being about 1.1 s−1 and 0.55, respectively. Sulfite has been chosen as a model to elucidate the electrocatalytic ability of NiPCNF-modified CCE prepared by one- or two-step sol-gel technique. The modified electrode showed excellent electrocatalytic activity toward the SO32− electro oxidation in pH range 3-9 in comparison with CCE modified by homogeneous mixture of graphite powder, Ni(NO3)2 and Na2[Fe(CN)5NO] (one-step sol-gel technique). Sulfite was determined amperometrically at the surface of this modified electrode in pH 7. Under the optimized conditions the calibration curve is linear in the concentration range 2 μM to 2.0 mM. The detection limit (signal-to-noise is 3) and sensitivity are 0.5 μM and 13.5 nA/μM. The modified carbon ceramic electrode containing nickel pentacyanonitrosylferrate shows good repeatability, short response time, t (90%) <2 s, long-term stability (3 months), and it is renewed by simple mechanical polishing and its immersing in Na2[Fe(CN)5NO] solution. The advantages of the SO32− amperometrically detector based on the nickel pentacyanonitrosylferrate-doped CCE is high sensitivity, inherent stability at wide pH range, excellent catalytic activity and less expense and simplicity of preparation. This sensor can be used as amperometric detector in chromatographic instruments. 相似文献
18.
S. Manandhar 《Electrochimica acta》2007,52(15):5010-5017
X-ray photoelectron spectroscopy (XPS) was used to study the spontaneous deposition of Pt and Ir on Ru(0 0 0 1). The spontaneous deposition experiments were performed in a combined ultra high vacuum/electrochemistry (UHV-EC) system allowing sample transport between UHV and electrochemical environments under controlled conditions. The Ru(0 0 0 1) electrode surface was cleaned in UHV and then brought into contact with either a Pt-containing solution(10 mM K2PtCl6 + 0.1 M H2SO4 or 10 mM (NH4)2PtCl4 + DI water) or with solutions containing 10 mM (NH4)2IrCl6 in varying concentrations of H2SO4 corresponding to pH values of 0.5, 1 and 7 in the electrochemistry chamber for 30 min without an externally applied potential. XPS data acquired after rinsing in DI water indicated that each metal is present in intermediate oxidation states. Pt is found spontaneously deposited as Pt(II) on Ru(0 0 0 1) at pH 1. Similarly, intermediate states of Ir are observed, with higher binding energies, characteristic of higher oxidation states, observed at higher pH values. Annealing the spontaneously deposited adlayer in UHV to >500 K in each case results in the reduction of the Pt or Ir adsorbate to the metallic state. Typical metal surface coverages, determined by XPS, varied with number of immersions and solution conditions, but in all cases was observed to be <0.3 monolayers average thickness. 相似文献
19.
Zhan Lin 《Electrochimica acta》2009,54(27):7042-9377
Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles directly onto electrospun carbon nanofibers. The morphology and size of Pt nanoparticles were controlled by the electrodeposition time. The resulting Pt/carbon composite nanofibers were characterized by running cyclic voltammograms in 0.20 M H2SO4 and 5.0 mM K4[Fe(CN)6] + 0.10 M KCl solutions. The electrocatalytic activities of Pt/carbon composite nanofibers were measured by the oxidation of methanol. Results show that Pt/carbon composite nanofibers possess the properties of high active surface area and fast electron transfer rate, which lead to a good performance towards the electrocatalytic oxidation of methanol. It is also found that the Pt/carbon nanofiber electrode with a Pt loading of 0.170 mg cm−2 has the highest activity. 相似文献
20.
Yasemin Oztekin Mutahire Tok Saliha Kiyak Zafer Yazicigil Arunas Ramanavicius 《Electrochimica acta》2010,56(1):387-395
Electrochemical modification of glassy carbon (GC) electrode by poly-4-nitroaniline (P4NA), electrochemical reduction of P4NA and applicability of electrode modified in this way for determination of copper(II) (Cu(II)) is reported in this study. Electrochemical surface modification was performed by cyclic voltammetry in the potential range between +0.9 V and +1.4 V vs. Ag/Ag+ (in 10 mM AgNO3) at the scan rate of 100 mV/s by 100 cycles in non-aqueous media. In order to provide electrochemical reduction of nitro groups on the P4NA-modified GC electrode surface (P4NA/GC), the cyclic voltammograms inducing/evidencing the reduction of nitro groups were performed in the potential range between −0.1 V and −0.8 V vs. Ag/AgCl/(sat.KCl) at the scan rate of 100 mV/s. The reduced P4NA/GC surfaces (Reduced-P4NA/GC) were treated with aqueous solution of nitrilotriacetic acid. The sensitivity of GC electrode modified in described way towards Cu(II) was investigated in Britton-Robinson buffer solution, pH 5.0. The potentiometric generic pulse technique was applied as innovative electrochemical method for detection of analytical signal. It was shown that GC electrodes modified in here described way will be suitable for the determination of Cu(II) in technological waste water and/or some other solutions containing Cu(II) ions. 相似文献