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1.
Theoretical relationships are developed to describe the open-circuit responses associated with the indirect laser-induced temperature-jump (ILIT) method, a method for measuring fast electron-transfer rate constants of surface-attached redox species. The analysis is also applicable to data obtained using the coulostatic charge-injection method. The unique relationship between km, the relaxation rate constant for the ILIT (or coulostatic) response, and Ei, the potential at which the system is initially poised, exhibits a surprising sensitivity to the values of k0, Ei0 (the standard rate constant and formal potential for the redox couple), α (the transfer coefficient in the Butler–Volmer equation) and γ (a dimensionless parameter which is directly proportional to the total surface concentration of the redox moiety). ILIT data for several examples of surface-attached ferrocene moieties confirm the theoretically predicted km vs Ei behavior. Values of Ei0 and γ extracted from the ILIT data agree well with the values obtained from cyclic voltammetric data thereby confirming that the ILIT and cyclic voltammogram (CV) experiments are sampling the same ferrocene population.  相似文献   

2.
A tungsten wire covered with Na0.75WO3 acts in potentiometry as a reversible pH electrode having a pH dependent open-circuit potential Eocp with nernstian slope. The mid-peak potential Emp of cyclic voltammograms also depends on pH. At low pH (e.g., pH 2) and slow scan rates (e.g., 2 mV s–1) the voltammetric response is almost completely reversible. At higher pH and faster scan rates, the voltammetric systems exhibit features of increasing irreversibility. Under the conditions of reversibility, the Eocp and Emp differ significantly. Eocp is determined by the proton transfer at the electrode surface; whereas Emp is determined by the electron transfer equilibrium tungsten(VI)/tungsten(V) and the proton transfer at the electrode surface. The difference between Eocp and Emp provides the individual thermodynamic contributions of electron and proton transfer to the overall pH dependent redox electrode. This is the first time that both contributions can be separated for an insertion electrochemical system (thin surface layer). It is also shown for the first time that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry.  相似文献   

3.
In this study, a grafted polymer (GP) with ZnO nanoparticles (GP/ZnO NPs) was attached on the surface of glassy carbon electrode (GCE), in order to produce a new modified electrode (GP/ZnO NPs-GCE). The gamma irradiation method was used to grafted polystyrene (polymer) with acrylonitrile (monomer), while slow evaporation process was used to prepare the new modified electrode. The cyclic voltammetry (CV) of K4[Fe(CN)6] was used to study the electrochemical properties GP/ZnO NPs-GCE. The peak separation (ΔEpa-c) was 500 mV between the redox peaks of Fe(II)/Fe(III) in an aqueous solution of 1 M KCl and the current ratio of redox current peaks (Ipa/Ipc) was ≈ 1 for the modified electrode. This indicated that the modified electrode has s good reversibility and conductivity, wherefore; it was applied in the voltammetric filed. It was found that the modified electrode GP/ZnO NPs-GCE have a reasonable solubility and stability at various pH medium. Additionally, the sensitivity of the electrochemical analysis by cyclic voltammetric (CV) method is extensively subjected to the pH medium and the scan rate (SR). A couple of redox current peaks of K4[Fe(CN)6] in KCl solution was observed with a reversible process: Fe3+/Fe2+. Finally a good diffusion coefficient of electroactive species (D) for the new modified electrode was found in this study by chronoamperometry method using Cottrell equation.  相似文献   

4.
The kinetic behaviour of a two-step sequential reaction including a 2nd order adsorption process is treated theoretically in the case of semiconductor electrodes. It is shown that the electronic structure of the semiconductor can be taken into account in some simplified cases by introducing a formal transfer coefficient comprised between 0 and 1 and potential independent. In both linear potential sweep voltammetry and steady state cyclic voltammetry, the usual characteristic features (EM, M, iM) of the voltammetric curves are calculated as a function of the sweep rate for different values of the transfer coefficient.  相似文献   

5.
The cyclic voltammetric and differential pulse polarographic behavior of cytochrome c3 of Desulfovibrio vulgaris, strain Miyazaki, has been evaluated in terms of a model employing four reversible redox centers. Both types of experiments can be fit by digital simulations using the four standard potentials: E10=?0.467, E20=?0.519, E30=?0.539 and E40=?0.580 V vs. SCE. The results are interpreted to mean that the four redox centers are chemically different and only weakly interacting. The relationships between the observed macroscopic standard potentials and the microscopic standard potentials for reduction of individual sites are discussed.  相似文献   

6.
The electrochemical properties of a gold electrode modified with a mixed thiol monolayer containing both a polar and a non-polar head group have been investigated in aqueous Fe(CN)64−, flavin adenine dinucleotide (FAD) and ubiquinone-0 (2,3-dimethoxy-5-methyl-1,4-benzoquinone, UQ0) solutions. The cyclic voltammetric current-potential (i-E) response of Fe(CN)64− was found to be affected considerably by the polarity of the head group contained in the mixed monolayer assembly, as compared with those of FAD and UQ0. It was also found that in the cases of UQ0 and FAD the i-E responses for the modified electrode were affected by their own molecular size rather than the polarity of the mixed monolayer head group. Furthermore, compared with Fe(CN)64− ion, these biologically related molecules are able to permeate readily into the well-organized and hydrophobic alkyl chains of the monolayer assembly. The voltammetric profile of UQ0 was improved by the modification of aminoethanethiol, as compared with those of bare gold and the electrode modified with other polar thiols. Further, two different permeation paths of the electrode species into the mixed monolayer are suggested from the variation of the i-E response with the cycle of the potential scan.  相似文献   

7.
The dominant voltammetric response of a yeast suspension in neutral or slightly alkaline media can be assigned to the redox transformations of nicotinamide adenine dinucleotide (NAD+/NADH) and nicotinamide adenine dinucleotide phosphate (NADP+/NADPH). By immobilization of yeast on platinum, a stable electrode can be prepared which shows an electrocatalytic activity towards the reduction of NADP+ and the reoxidation of the product formed. Reversible cyclic voltammetric responses were obtained. The peak currents depend practically linearly on the NADP-Na2 concentration and on the square root of the scan rate. The surface mass changes accompanying the redox transformations were monitored by an electrochemical quartz crystal nanobalance.  相似文献   

8.
Highly boron-doped diamond electrodes are characterized voltammetrically employing Ru(NH3)63+/2+, Fe(CN)63−/4−, benzoquinone/hydroquinone, and cytochrome c redox systems. The diamond electrodes, which are polished to nanometer finish, are initially `activated' electrochemically and then pretreated by oxidation, reduction, or polishing. All electrodes give reversible cyclic voltammetric responses for the reduction of Ru(NH3)63+ in aqueous solution.Redox systems other than Ru(NH3)63+/2+ show characteristic electrochemical behavior as a function of diamond surface pretreatment. In particular, the horse heart cytochrome c redox system is shown to give reversible voltammetric responses at Al2O3 polished boron-doped diamond electrodes. No voltammetric response for cytochrome c is detected at anodically pretreated diamond electrodes. The observations are attributed to preferential interaction of the polished diamond surface with the reactive region of the cytochrome c molecule and low interference due to a lack of protein electrode fouling.  相似文献   

9.
A new voltammetric sensor based on electropolymerization of glycine at glassy carbon electrode (GCE) was developed and applied to determine of pyrazinamide (PZA) by square-wave voltammetry (SWV). The initial cyclic voltammetric studies showed an electrocatalytic activity of poly(Gly)/GCE on redox system of pyrazinamide in 0.1 mol L?1 phosphate buffer solution pH 7.5, with E Pc and E Pa in ?0.85 and ?0.8 V (versus E Ag/AgCl), respectively. Studies at different scan rates suggest that the redox system of pyrazinamide at poly(Gly)/GCE is a process controlled by diffusion in the interval from 10 to 100 mV s?1. Square-wave voltammetry-optimized conditions showed a linear response of PZA concentrations in the range from 0.47 to 6.15 μmol L?1 (R?=?0.998) with a limit of detection (LOD) of 0.035 μmol L?1 and a limit of quantification (LOQ) of 0.12 μmol L?1. The developed SWV-poly(Gly)/GCE method provided a good intra-day (RSD?=?3.75 %) and inter-day repeatability (RSD?=?4.96 %) at 4.06 μmol L?1 PZA (n?=?10). No interference of matrix of real samples was observed in the voltammetric response of PZA, and the method was considered to be highly selective for the compound. In the accuracy test, the recovery was found in the range of 98.2 and 104.0 % for human urine samples and pharmaceutical formulation (tablets). The PZA quantification results in pharmaceutical tablets obtained by the proposed SWV-poly(Gly)/GCE method were comparable to those found by official analytical protocols.  相似文献   

10.
吕亚芬  蔡称心 《化学学报》2006,64(24):2396-2402
将来源于Spinacia Oleracea的铁氧化还原蛋白(ferredoxin, SOFd)固定在多壁碳纳米管(CNT)表面, 紫外-可见及红外光谱表明, SOFd在CNT表面没有变性, 仍保持原来的二级空间结构. 循环伏安结果表明, SOFd在CNT表面能进行有效和稳定的直接电子转移反应, 伏安曲线上出现一对良好的、几乎对称的氧化还原峰, 式量电位E0'为(-570.4±1.5) mV (vs. SCE, 0.1 mol/L磷酸盐缓冲液), 且不随扫速和溶液pH值的变化而变化. SOFd直接电子转移的表观速率常数ks为(0.73±0.04) s-1.  相似文献   

11.
The reduction of microcrystalline C60 fullerene, adhered at a carbon electrode and immersed in aqueous electrolyte, has been studied under various voltammetric conditions. This work reports mainly the voltammetric studies carried out principally in electrolyte containing potassium ions. Comparison of adherence techniques, such as solvent casting and mechanical transfer methods, are made to assess if the type of adhered techniques has any significant influence on the observed electrochemistry. The solvent casting method is found to produce three peaks in the potential for C600/n- redox couple as compared to a single and large peak produced when a mechanical transfer technique is employed. When the reduction potential of microcrystalline C60 in the presence of K+ is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C600/n- redox couple during cyclic voltammetry is observed to change with concentration of the cations and the observed electrochemistry can be attributed to a cation-exchange mechanism. The reduction of C60 is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K n C60 fulleride, which does not appear to undergo dissolution is obtained under cyclic voltametric conditions. This coating remains electrochemically active in the presence of tetrabutylammonium ions in acetonitrile. Scan rate, chronocoulometric, and scanning electron microscopic studies provide evidence of the presence of a surface process involving solid–solid transformation.  相似文献   

12.
The standard redox electrode potential (E°) values of metallocene compounds are obtained theoretically with density functional theory (DFT) method at B3LYP/6-311++G(d,p) level and experimentally with cyclic voltammetry (CV). The theoretical E° values of metallocene compounds are in good agreement with experimental ones. We investigate the substituent effects on the redox properties of metallocene compounds. Among the four metallocene compounds, the E° values is largest for titanocene dichloride and smallest for ferrocene.  相似文献   

13.
Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k0) of the s-tetrazine molecules and Li-ion diffusivity (DLi) in the s-tetrazine electrodes are much faster than conventional electrode active materials.  相似文献   

14.
The electrochemical behaviour of tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate (Ru(II)) microparticles, immobilised on a graphite electrode and adjacent to an aqueous electrolyte solution, has been studied by cyclic voltammetry and an in situ spectroelectrochemical technique. The solid Ru(II) complex exhibits one reversible redox couple with a formal potential (Ef) of 1.1 V versus Ag¦AgCl. The continuous cyclic voltammetric experiments showed that the Ru(II) microparticles are stable during the electrochemical conversions. The in situ spectroelectrochemical study showed that the absorbance at 463 nm decreased due to the oxidation of Ru(II) to Ru(III). Upon reduction, the growth of absorbance at 463 nm was observed due to the formation of Ru(II) complex and this process was reversible.  相似文献   

15.
《Electroanalysis》2003,15(1):19-25
The electrochemical behavior of 2‐(5‐amino‐ 1,3,4‐oxadiazolyl)‐5‐nitrofuran (NF359) and its comparison with well‐known drugs such as nifurtimox (NFX) and nitrofurazone (NFZ) in protic, mixed and aprotic media by cyclic voltammetry, tast and differential pulse polarography was studied. All the compounds were electrochemically reducible in all media being the reduction of the nitrofuran group the main voltammetric signal. The one‐electron reduction couple due to the nitro radical anion formation was visualized in mixed (for NF359 and NFZ) and aprotic media (for all compounds). By applying a cyclic voltammetric methodology we have calculated the decay constants (k2) of the corresponding nitro radical anions in mixed and aprotic media. In mixed medium data fit well with a disproportionation reaction of the nitro radical anion but in aprotic medium fit better with a dimerization reaction. Also, considering cyclic voltammetric measurements in aprotic media we have estimated the reduction potential of the RNO2/RNO2.? couple in aqueous medium, pH 7 (E17 values) finding very good correlation with E17 values obtained by pulse radiolysis. Furthermore we have calculated the equilibrium constants from the electron transfer from nitro radical anion to oxygen (kO2) finding that nitro radical anion from NF359 is thermodynamically favored to react with oxygen in respect to both NFZ and NFX.  相似文献   

16.
A novel competitive binding assay was implemented to monitor the binding of a redox inactive substrate to a redox inactive metallacrown host based on its competition with ferrocene carboxylate (FcC?) using cyclic voltammetry (CV). First, the binding of FcC? to LnIII[15‐MC‐5] (LnMC) hosts was characterized by cyclic voltammetry. It was shown that the voltammetric half wave potentials, E1/2, shifted to more positive potentials upon the addition of LnMC. The explicit dependence of E1/2 with the concentration of LnMC was used to determine the association constants for the complex. The FcC? binding strength decreased with larger central lanthanide metals in the LnMC hosts, and substantially weaker binding was observed with LaIII. X‐ray crystallography revealed that the hydrophobic host cavity incompletely encapsulated FcC? when the guest was bound to the nine‐coordinate LaIII, suggesting the LnMC’s ligand side chains play a substantial role in guest recognition. With knowledge of the MC‐FcC? solution thermodynamics, the binding affinity of a redox inactive guest was then assessed. Addition of sodium benzoate to a LnMC and FcC? mixture resulted in E1/2 shifting back to the value observed for FcC? in the absence of LnMC. The association constants between benzoate and LnMC’s were calculated via the competitive binding approach. Comparison with literature values suggests this novel assay is a viable method for determining association constants for host–guest systems that exhibit the proper electrochemical behavior. Notably, this CV competitive binding approach does not require the preparation of a modified electrode or a tethered guest, and thus can be generalized to a number of host–guest systems.  相似文献   

17.
Rate laws presented to date for analysis of a.c. cyclic voltammetric data have invoked the so-called “slow scan limit approximation” which requires that ΔEω ? v, where Δ E and ω are the applied a.c. potential amplitude and angular frequency, respectively, and v is the d.c. potential scan rate. To provide a more useful guideline for the experimentalist than this qualitative condition, a pure digital simulation approach has been used to compute the a.c. cyclic time domain waveform for a reversible process under small amplitude conditions. The a.c. content of this waveform is extracted by the digital FFT alogirthm. Results of this study are presented here. Among the conclusions reached are more quantitative limitations for the slow scan limit rate laws describing the fundamental and second harmonic responses (approximately 128 a.c. cycles/d.c. cyclic sweep and 512 a.c. cycles/d.c. cyclic sweep, respectively) and an interesting prediction that the latter limitations can be relaxed further by a current waveform subtraction strategy, to as low as about 16 a.c. cycles/d.c. cyclic sweep for the fundamental and second harmonics. The cycles/sweep values assume one triangular wave potential scan of ±200 mV is encompassed.  相似文献   

18.
A new grafted polymer electrode (GPE) (polystyrene as polymer) was grafted with acrylonitrile as a monomer using gamma irradiation to produce a new grafted polymer. The redox process of K3Fe(CN)6 during cyclic voltammetry was studied by the new GPE. The ratio of Ipc/Ipa >1 of GPE to GCE Ipc/Ipa = 1.7, indicating that this electrode is a reversible electrode and can be used in conductivity studies by voltammetric analysis. The physical properties of the new electrode GP have good hardness, insolubility, and stability at different high temperatures and at different pH. Also, the sensitivity under conditions of cyclic voltammetry is significantly dependent on pH, electrolyte, and scan rate. At different scan rates, two oxidation peaks and two reduction peaks of Fe(III) were observed in a reversible process: Fe(III) Fe(II), and Fe(II) Fe(0). Interestingly, the redox reaction of Fe(III) solution using GPE remained constant even after 15 cycles. It is therefore evident that the GPE possesses some degree of stability. The potential use of the grafted polymer as a useful electrode material is therefore clearly evident.  相似文献   

19.
A measurement approach is described and data are presented which demonstrate the ability to effect a.c. cyclic voltammetric measurements with the on-line digital FFT approach to faradaic admittance data acquisition. The equipment utilized enables complete faradaic admittance spectra to be obtained at an effective spectrum acquisition rate of 10 s?1, so that the d.c. potential range encompassed by a typical cyclic wave can be encompassed with adequate resolution in the Edc dimension in ≥6 s, approximately. The instrument features dynamic, computerized measurement and compensation of the non-faradaic ohmic resistance and double-layer capacitance contributions to the acquired total cell admittance. Measurements with quasi-reversible systems yield the expected faradaic admittance and phase angle responses over a quite generous bandwidth. Applications to mercury and platinum electrodes are illustrated.  相似文献   

20.
Neutral red was directly electropolymerized onto the carbon nanotubes modified electrode. A polymerized neutral red/carbon nanotubes composite film was characterized by scanning electron micrograph (SEM) and cyclic voltammetry (CV). Well‐defined voltammetric responses are observed for [Fe(CN)6]4?/3? on the composite film modified glassy carbon electrode. And it's found that this modified electrode has good catalysis on the redox of rutin. Differential pulse voltammetry method was used to determinate the concentration of rutin and obtain a linear equation between the current and concentration in a certain range. The modified electrode is satisfied with us for its good sensibility and stability.  相似文献   

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