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1.
The kinetics of the p-benzoquinone/hydroquinone Q/QH2 couple on a platinum electrode are analysed on the basis of the theory presented earlier (E. Laviron, J. Electroanal. Chem., 146 (1983) 15) for the nine-member square scheme when the protonations are assumed to be at equilibrium, using experimental data from the literature. The square scheme is of the NN type. The Tafel plots and the variations of the experimental apparent rate constants between pH 0 and 7 are in good agreement with the theoretical predictions. The heterogeneous rate constants found for the elemental electrochemical steps are as follow: Q Q?, kh3=1/6×10?3 cm s?1; QH.QH?, kh5=0.11 cm s?1; QH+QH., kh2?160 cm s?1; kh4 for the reaction QH2+.QH2 is in the range 0.5–4 cm s?1. Between pH 0 and 7, the reaction sequence during the reduction is, for the most part, successively H+e?H+e?, e?H+H+e?, and e?H+e?H+ (reverse sequence during the oxidation).  相似文献   

2.
The electrochemical kinetics of the benzoquinone (Q)/hydroquinone (H2Q) redox couple at platinum electrodes in aqueous solutions has been found to be extremely sensitive to the nature of species adsorbed on the electrode surface at monolayer coverages. Experimental measurements were based on thin-layer cyclic voltammetry; the use of thin-layer electrodes was dictated by the need to minimize surface contamination. Bulky neutral or anionic aromatic adsorbates led to the familiar U-shaped rate-vs.-pH curves; the rate minimum occurred near pH 4. Kinetic effects due to oriental changes of chemisorbed species were noted only when the rate was low. Adsorbed 1 atoms led to comparatively rapid reactivity (rate constant k° > 10?3 cm s?1) and virtual independence of pH. Profound retardation resulted from pretreatment ofthe surface with CN? and SCN?; total irreversibility (k° < 10?6 cm s?1) was observed at pH 4, with a further decrease in rate at pH 7. In contrast, when the surface contained n layer of chemisorbed phenyltriethylammonium cations, the electrode rate increased with increasing pH. The results indicate that different reaction pathways predominate when different absorbates are present.  相似文献   

3.
Functionalized polypyrrole films were prepared by incorporation of Fe(CN)6 3− as doping anion during the electropolymerization of pyrrole at a glassy carbon electrode from aqueous solution. The electrochemical behavior of the Fe(CN)6 3−/Fe(CN)6 4− redox couple in polypyrrole was studied by cyclic voltammetry. An obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole film with ferrocyanide incorporated was demonstrated by oxidation of ascorbic acid at the optimized pH of 4 in a glycine buffer. The catalytic effect for mediated oxidation of ascorbic acid was 300 mV and the bimolecular rate constant determined for surface coverage of 4.5 × 10−8 M cm−2 using rotating disk electrode voltammetry was 86 M−1 s−1. Furthermore, the catalytic oxidation current was linearly dependent on ascorbic acid concentration in the range 5 × 10−4–1.6 × 10−2 M with a correlation coefficient of 0.996. The plot of i p versus v 1/2 confirms the diffusion nature of the peak current i p. Received: 12 April 1999 / Accepted: 25 May 1999  相似文献   

4.
The electro chemical systems of chloranil (quinone/semiquinone and semiquinone/hydroquinone) are shown to be usable as pH indicators in anhydrous hydrogen fluoride and in the superacid mixtures HF + MFn (where MFn = PF5, BF3, TaF5, NbF5, AsF5 and SbF5). The combined use of both hydrogen and chloranil electrodes has allowed the establishment of a complete potential-pH diagram of chloranil in the whole acidity range of HF. The quinone/semiquinone system can be used at very high acidity levels (solutions of AsF5 or SbF5) where the hydrogen electrode does not function correctly. A new value of the autoprotolysis constant of HF is reported (Ki = [H+. [F-] = 10-13.7 mol2 l-2) and compared with earlier values. The equilibrium constants of acid-base systems of the quinone (Q/QH+) and hydroquinone (QH2/QH3+ and QH2+4) forms of chloranil, and the disproportionation constant of the semiquinone (QH2+ form are also reported. The indicator system allows the acidity levels reached in HF to be placed on an R(H) scale (where R(H) = 0 corresponds to pH = 0 in aqueous solution). These levels were found to lie between R(H) = -14.2 for 1 M KF solution and R(H) = -27.9 for 1 M SbF5 (i.e. 18% by weight).  相似文献   

5.
The standard electrode potential for the quinone (Q)-hydroquinone (QH2) couple in aqueous acidic media has been explicitly calculated. Molecular geometries of Q and QH2 have been optimized. Protonation of Q, i.e., the formation of QH+ and QH, have been considered. Molecular geometries of these species have been thoroughly optimized. The energy of complexation of these molecules with water have been calculated by optimizing the structures of the hydrated complexes Q · 6H2O, QH2 · 6H2O, QH+ · 6H2O. and QH · 6H2O. The ion–solvent interaction energy of QH+ · 6H2O, in turn, has been calculated by considering the complex QH+ · 6H2O…? 2H2O, where the two extra water molecules approach the charge center of the complex QH+ · 6H2O vertically from top and bottom of the quinonoid ring. The standard reduction potential calculated by the CNDO method, 0.8548 V, is somewhat larger than the experimental potential, 0.6998 V, at 25°C. But the INDO value, 0.7085 V, is in excellent agreement with the observed potential. The electrode potential for the plastoquinone (PQ)-plastohydroquinone (PQH2) couple present in the aqueous pool in chloroplast has been calculated by the INDO method. The basic geometries of PQ, PQH+, and PQH2/sb have been synthesized by adopting the optimized geometries of Q, QH+, and QH2 and considering methyl substituents as well as an isoprenoid side chain containing up to 3 isoprene units with possible geometrical isomerism. The hydrated species PQ · 6H2O, PQH+ · 6H2O, and PQH2 · 6H2O are unstable compared to the isolated species PQ, PQH+, and PQH2, respectively. In fact, we have found that the hydration of PQH+ and PQH2 is much less extensive, and stability arises only when the hydroxyl groups in these two molecules are hydrogen-bonded to water molecules. But PQH+ is also stabilized through the association of two more water molecules in the vertical direction. For this reason, we have calculated the reduction potential of the PQ/PQH2 system from the energies of the isolated molecules PQH2 and the hydrated species PQH+ · 2H2O. The computed standard reduction potential is 0.2785 V and it yields a potential of 0.07V at pH 7 at 25°C, which is in good agreement with the reduction potential 0.11 V observed for plastoquinone in the aqueous pool in chloroplast. © 1994 John Wiley & Sons, Inc.  相似文献   

6.
《Electroanalysis》2006,18(7):703-711
A simple procedure was developed to prepare a glassy carbon electrode modified with carbon nanotubes (CNTs) and thionin. Abrasive immobilization of CNTs on a GC electrode was achieved by gently rubbing the electrode surface on a filter paper supporting carbon nanotubes, then immersing the GC/CNTs‐modified electrode into a thionin solution (electroless deposition) for a short period of time (5–50 s for MWCNTs and 5–120 s for SWCNTs ). Cyclic voltammograms of the resulting modified electrode show stable and a well defined redox couple with surface confined characteristic at wide pH range 2–12. The electrochemical reversibility and stability of modified electrode prepared with incorporation of thionin into CNTs film was compared with usual methods for attachment of thionin to electrode surfaces such as electropolymerization and adsorption on the surface of preanodized electrodes. The formal potential of redox couple (E°′) shifts linearly toward the negative direction with increasing solution pH. The surface coverage of thionin immobilized on CNTs glassy carbon electrode was approximately 1.95×10?10 mol cm?2 and 3.2×10?10 mol cm?2 for MWCNTs and SWCNTs, respectively. The transfer coefficient (α) was calculated to be 0.3 and 0.35 and heterogeneous electron transfer rate constants (Ks) were 65 s?1 and 55 s?1 for MWCNTs/thionin and SWCNTs/thionin‐modified GC electrodes, respectively. The results clearly show a great facilitation of the electron transfer between thionin and CNTs adsorbed on the electrode surface. Excellent electrochemical reversibility of redox couple, high stability, technically simple and possibility of preparation at short period of time are of great advantages of this procedure for modification of electrodes.  相似文献   

7.
Sulphur dioxide is preconcentrated from air into a polydispersed aerosol of water. The aerosol condenses on impact on the detector, on the surface of which a film of the condensate is maintained. The conductance of the liquid film is measured with a pair of platinum electrodes. The calibration dependence is nonlinear but corresponds to the theoretical model. The concentration range 0.05–2.2 mg SO2 m−3 was studied. The detection limit was 2 × 10−3 mg m−3; the relative standard deviation for 0.38 mg m−3 was 2.4%. A steady-state response to a change in SO2 concentration was attained within ca. 70 s. Ammonia is the only interferent.  相似文献   

8.
The electrochemical properties of FAD adsorbed on graphite were studied with cyclic voltammetry. A film with a surface coverage of up to 2×10?8 mol cm?2 was formed after 4 h. The film-covered electrodes were stable for long times and they were investigated in buffers without any FAD. A single well-behaved wave was observed, k0≌1 s?1. The pH dependence of E1/2 was studied. On glassy carbon, platinum and gold much less FAD was adsorbed and it was removed with one rinse.  相似文献   

9.
The electrochemical behavior of 5-amino-1,10-phenanthroline and tris[5-amino-1,10-phenanthroline]-iron(II) at carbon paste, glassy carbon, and platinum electrodes is reported. The iron complex undergoes electrochemically induced oxidative polymerization from acetonitrile solutions and the resulting polymers are very stable. Charge transport through the polymer films occurs with a charge transfer diffusion coefficient, Dct, equal to 3.1 × 10−8 cm2 s−1 corresponding to an electron self-exchange rate of 5.2×107M−1 s−1. The activation energy and the entropy change for the charge transfer diffusion process are (approximate values) 32.0 ± 0.12 kJ mol−1 and −24.7 ± 0.4 J K−1 mol−1, respectively.  相似文献   

10.
Jiang XE  Guo LP  Du XG 《Talanta》2003,61(3):247-256
Electrochemistry and electrocatalysis of binuclear cobalt phthalocyaninehexasulfonate sodium salt (bi-CoPc) were investigated successfully in liquid crystal films of didodecyldimethylammonium bromide (DDAB) on pyrolytic graphite (PG) electrodes in aqueous solution. This new bi-CoPc-surfactant film modified electrode could reduce aggregation of bi-CoPc in aqueous solution, which was confirmed by the electronic absorption spectra in the visible region and images of transmission electron microscopy (TEM). The charge transport diffusion coefficient (Dct) and apparent heterogeneous electrode reaction rate constant (ks) for this modified electrode were estimated. The reduction of bi-CoPc ligand showed excellent electrocatalytic ability for the reduction of trichloroacetic acid (TCA) and catalytic current had a linear relationship with the concentration of TCA in the range of 3×10−5-7.5×10−3 M. The reduction of bi-Co(III)Pc/bi-Co(II)Pc couple exhibited new pattern of catalytic reactivity in the reduction of oxygen. Peak current for the cathodic reduction of oxygen is proportion to the square root of the scan rate in the range of 5-1000 mV s−1 in oxygen-saturated solution.  相似文献   

11.
《先进技术聚合物》2018,29(1):401-406
Polypyrrole films on fluorine doped tin oxide (FTO)‐coated glass substrate were prepared in situ by placing FTO/glass substrates where pyrrole was polymerized by methyl orange‐ferric chloride complex. The atomic force microscopy image indicated growth of acicular nanorods of polypyrrole. These films exhibited catalytic activity towards I3/I redox couple and have been investigated for counter electrode application in dye‐sensitized solar cell (DSSC). The fabricated DSSC with N719 dye/TiO2 as photoanode, and PPy/FTO as counter electrode shows ~1.7% efficiency.  相似文献   

12.
Polypyrrole has been electrodeposited at a constant current density of 4 mA cm−2 onto Pt from 0.1 M pyrrole, 0.1 M NBu4 BF4 in dry CH3CN. The thickness of the polypyrrole has been varied over a wide range of 0.02 to 50 μm. Elemental analysis reveals an excess of hydrogen in the polymer. The electrochemical equivalent corresponds to an insertion of 25–35 mole % BF4-anions and a current efficiency of 80–100% for the electrodeposition process. SEM technique shows a highly textured material at a thickness larger than 1 μm. Reversible water vapour adsorption of this material has been detected. The potential/time curve during galvanostatic electrodeposition is without special features. The start potential, USSCE = 0.9 V, is relatively negative. A slight decay of potential in the course of the electrodeposition of thick layers is explained in terms of increasing surface roughness. Cyclic voltammetry has been used for a systematic investigation into the role of the positive and negative endpotentials. The importance of a total primary discharge after electrodeposition has been clarified. At a film thickness d exceeding 1 μm, the cyclovoltammetric curve degenerates, and the anodic peak flattens and shifts to more positive potentials. Active mass utilization decreases with increasing d and with increasing voltage scan rate vs. The plot of anodic peak current density vs. vs is linear for layers below 1 μm thickness. For thick layers and at high vs, deviations occur, indicating a transport limitation in the film. As the film is not homogeneous, a quantitative evaluation is not possible.  相似文献   

13.
Potential cycling was used for oxidation of NAD+ and producing an electroactive redox couple which strongly adsorbed on the electrode surface modified with single walled carbon nanotubes (SWCNTs). Modified electrode shows a pair of well defined and nearly reversible redox peaks at pH range 1–13 and the response showed a surface‐controlled electrode process. The surface coverage and heterogeneous electron transfer rate constant (ks) of adsorbed redox couple onto CNTs films were about 6.32×10?10 mol cm?2 and 2.0 (±0.20) s?1, respectively, indicating the high loading ability of CNTs toward the oxidation product of NAD+ (2,8‐dihydroxy adenine dinucleotide) and great facilitation of the electron transfer between redox couple and CNTs immobilized onto electrode surface. The modified electrode exhibited excellent electrocatalytic activity for H2O2 reduction at reduced overpotential. The catalytic rate constant for H2O2 reduction was found to be 2.22(±0.20)×104 M?1 s?1. The catalytic reduction current allows the amperometric detection of H2O2 at an applied potential of ?0.25 V vs. Ag/AgCl with a detection limit of 10 pM and linear response up to 100 nM and resulting analytical sensitivity 747.6 nA/pM. The remarkably low detection limit (10 pM) is the lowest value ever reported for direct H2O2 determination on the electrodes at pH 7. The modified electrode can be used for monitoring H2O2 without the need for an enzyme or enzyme mimic. The proposed method for rapid amperometric detection of H2O2 is low cost and high throughput. Furthermore, the sensor can be used to any detection scheme that uses enzymatically generated H2O2 as a reactive product in biological systems.  相似文献   

14.
The phenomenon of catalytic hydrogen evolution in the presence of platinum salts on the epoxy-resin-impregnated graphite-based mercury film electrode was studied. Two measurements were performed: (i) the deposition of catalyst on the IGE surface from HCl solution containing H2PtCl6 and HgCl2; (ii) the voltammetric curve of a solution of HCL + KCl was recorded. The effect of some parameters on the catalytic hydrogen evolution peak potential was studied. The investigations performed have shown that the four following parameters have a decisive effect on the form of the CHE curve: (1) Hg2+ concentration in the deposition step; (2) deposition potential value; (3) deposition time; (4) Pt(IV) concentration during the deposition step. It was established that, with increasing amount of Pt deposited on the IGE, a considerable shift of the CHE peak potential towards positive values occurred. A linear potential dependence of the CHE peak on log cPt was obtained when the Pt(IV) concentration was changed from 4×10−9M to 2×10−6M. That dependence can be employed well for analytical purposes.  相似文献   

15.
Combined measurements of piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance spectrum (EIS) using a suitable isolation capacitance is reported for the first time to monitor in situ adsorption and acidic denaturation of human serum albumin (HSA) on gold electrodes in Britton-Robinson (B-R) buffers. This method provides simultaneously mutual-interference-free and accurate parameters of EIS and PQCI. Effects of surface thiol-modification, electrode-potential and solution pH on HSA adsorption were examined and discussed. Comparative experiments of HSA adsorption in a B-R buffer of pH 6.42 on bare, cysteine- and 1-dodecanethiol-modified gold electrodes revealed that HSA adsorption is more significant on a hydrophobic (1-dodecanethiol-modified) surface. Insignificant electrode-potential effect implied minor electrostatic effects on HSA adsorption. The adsorption amount of HSA at pH 3.28 was found to be notably greater than those at pH 4.84 and 6.42. To characterize HSA adsorption, electrode standard rate constants (ks) of the Fe(CN)63−/Fe(CN)64− couple were measured before and after HSA adsorption. The ks-pH curves on an HSA-modified Au electrode revealed that ks increased abruptly with the decrease of solution pH below pH ∼4. Moreover, pH-dependent responses of the resonant frequency, the motional resistance, the double-layer capacitance, the capacitance of adsorbed HSA layer and the peak absorbance of HSA solutions at 278 nm all exhibited an inflexion change at pH ∼4, and these findings have been explained on the basis of acidic denaturation of HSA and electrical charges carried by HSA molecules.  相似文献   

16.
电化学合成聚吡咯(PPy)时,聚合电解液的pH 值对PPy 薄膜的形貌和性质有较大的影响,进而影响PPy薄膜对I-/I3-的电催化活性以及基于PPy对电极(CE)的染料敏化太阳电池(DSSCs)的光电转换性能. 本文采用电化学恒电位方法,在掺杂氟的SnO2(FTO)导电玻璃上合成出了对甲苯磺酸根离子掺杂的聚吡咯(PPy-TsO)电极,并将其作为DSSCs 的对电极. 通过改变吡咯聚合时聚合电解液的pH值,借助扫描电镜(SEM)、紫外-可见(UV-Vis)吸收光谱、X-射线光电子能谱(XPS)和循环伏安(CV)等表征技术,详细探讨了聚合溶液pH值对PPy CE形貌、结构及其对I-/I3-的电催化性能的影响. 研究发现在pH 2.0下合成的聚吡咯对阴离子掺杂率最高且链共轭性最佳,具有对I-/I3-氧化还原介质最强的催化能力,基于此PPy CE的电池光电转化效率也最高.pH 值太大或太小都不利于生成具有高掺杂率和高催化活性的PPy电极,组装成DSSCs后的光电转换效率也较低.  相似文献   

17.
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   

18.
《Electroanalysis》2003,15(8):733-738
The electrochemical properties of gold electrode surfaces modified by molybdenum oxide films intercalated with platinum microparticles have been described. The incorporation of Pt microparticles at the oxide film was characterized by PIXE (particle induced X‐ray emission) spectroscopy. The modified electrode showed electrochemical activity at around ?0.5 V in 50 mmol L?1 Na2SO4 supporting electrolyte (pH 3), corresponding to the reduction of protons at platinum sites and further transfer of hydrogen atoms to form reduced molybdenum oxides (bronzes). At 0.1 V, the MoO3 / Pt electrode showed a better performance for hydrogen peroxide oxidation than on platinized gold electrodes. The solution pH has a marked effect on the voltammetric profile and best responses for hydrogen peroxide were obtained at the 5.0 to 6.0 pH range. The activation of the electrode by polarization at negative potentials was also studied and a mechanism by which more platinum sites are available as a consequence of this process was proposed. Calibration plots for hydrogen peroxide were highly linear (r=0.9989) in the 0.2 to 1.6 mmol L?1 concentration range, with a relative standard deviation (RSD)<1%.  相似文献   

19.
A Nickel Schiff base complex, insoluble in water, was synthesized and used as modifier. A Nickel Schiff base modified carbon paste electrode MCPE was build. The electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-Ray spectroscopy (EDXS), cyclic voltammetry and chronoamperometry. The modifier is elctroactive, a well defined redox couple of NiIII/NiII in alkaline medium was made in evidence. It presents a quasi-reversible system with electron transfer coefficient (0.38) and electron transfer rate of 4.5 s−1. The electrogenerated NiIII species on the surface of the electrode act as an excellent catalyst toward thiosulfate oxidation reaction with a chemical rate constant Kh equal to 23,6 M−1s−1. The different techniques involved in this study qualify our modified electrode as sensitive, reliable and very stable for thiosulfate analysis.  相似文献   

20.
The electrochemical properties of violuric acid (VA) have been investigated at pH 4.0–10.0 by using cyclic voltammetry on a glassy carbon electrode. The peak current was proportional to the square root of the potential scan rate. The calculated diffusion coefficient was 2.0±0.7×10−6 cm2 s−1. The formal oxidation–reduction potential of VA was 0.63 V versus SCE at pH 7.0. The kinetics of VA interaction with reduced glucose oxidase (GO) was explored in the electrocatalytical system. A typical electrocatalytical wave was generated in the presence of the VA and glucose. An apparent kox calculated by using the Nicholson–Shain function was 1.85×106 M−1 s−1 at pH 7.0 and 25 °C. Glucose and l-lactate bioelectrodes were prepared by adsorbing the GO and l-lactate oxidase (LO) onto the VA-modified graphite electrode. The electrode was poised at 0.6 V versus SCE and linear response was obtained over the range of 4–20 mM glucose and 2–12 mM l-lactate, respectively.  相似文献   

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