首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 62 毫秒
1.
The structures and the electrochemical characteristics of La0.7−x CexMg0.3Ni2.8Co0.5 (x = 0.1–0.5) alloy, Ti0.25−x ZrxV0.35Cr0.1Ni0.3 (x = 0.05–0.15) alloy and AB3<x<5-type alloy, which are the representative examples of AB3-type alloy, solid solution alloy and non-AB5-type alloy, respectively, have been investigated, and the performances of MH-Ni battery in which AB3<x<5 type alloy is used as the negative electrode material are examined at relatively low temperature.  相似文献   

2.
The effects of Co alloying to Pt catalyst and Nafion pretreatment by NaClO4 solution on the rate-determining step (RDS) of oxygen reduction at Nafion-impregnated Pt-dispersed carbon (Pt/C) electrode were investigated as a function of the potential step ΔE employing potentiostatic current transient (PCT) technique. For this purpose, the cathodic PCTs were measured on the pure Nafion-impregnated and partially Na+-doped Nafion-impregnated Pt/C and PtCo/C electrodes in an oxygen-saturated 1 M H2SO4 solution and analyzed. From the shape of the cathodic PCTs and the dependence of the instantaneous current on the value of ΔE, it was confirmed that oxygen reduction at the pure Nafion-impregnated electrodes is controlled by charge transfer at the electrode surface mixed with oxygen diffusion in the solution below the transition potential step |ΔE tr| in absolute value, whereas oxygen reduction is purely governed by oxygen diffusion above |ΔE tr|. On the other hand, the RDS of oxygen reduction at the partially Na+-doped Nafion-impregnated electrodes below |ΔE tr| is charge transfer coupled with proton migration, whereas above |ΔE tr|, it becomes proton migration in the Nafion electrolyte instead of oxygen diffusion. Consequently, it is expected in real fuel cell system that the cell performance is improved by Co alloying since the electrode reaches the maximum diffusion (migration) current even at small value of |ΔE|, whereas the cell performance is aggravated by Nafion pretreatment due to the decrease in the maximum diffusion (migration) current.  相似文献   

3.
In this paper, the preparation conditions of antimony-doped SnO2 and PbO2 electrode were optimized for the degradation activity of AO7 dye solution. The results showed that when the doping content of Sb is 8 mol %(SnO2-Sb(0.08)), the SnO2 electrode exhibited best activities for the decolorization and mineralization of AO7. The concentration of NaF in electroplating solution had a noticeable effect on PbO2 electrode for the decolorization of AO7 solution, but little influence on the COD removal rate. The anodic stability tests showed that the electrode prepared in the solution containing 0.10 g l−1 NaF (PbO2-F(0.10)) was best for environmental application. The comparison of SnO2-Sb(0.08), PbO2-F(0.10) and Boron-doped Diamond (BDD) electrodes revealed that a more rapid decolorization rate was obtained on SnO2-Sb(0.08) and PbO2-F(0.10) electrodes in dilute AO7 solutions, while higher COD removal rate of concentrated AO7 solutions was on BDD and SnO2-Sb(0.08) electrodes. The effect of concentration of Na2SO4 on the degradation rate of AO7 was very notable on BDD electrode for its highest overpotential of oxygen evolution reaction. In the chloride-containing medium, the decolorization was accelerated greatly but the completed mineralization of AO7 was inhibited with the increasing of chloride ions concentration when these high-overvoltage anodes were used Published in Russian in Elektrokhimiya, 2008, vol. 44, No. 7, pp. 865–875. The text was submitted by the authors in English.  相似文献   

4.
For the first time, the positive carbon rod of zinc-carbon battery (battery carbon rod electrode, BCRE) was used as a new working electrode and its electrochemical behavior was compared with carbon paste and glassy carbon electrodes in KCl solution containing Fe(CN6)3–/4– ions as probe agent. Then, the sponge/raspberry-like Au nanoclusters (AuNCs) were synthesized on BCRE by one-step electrodeposition of HAuCl4 in phosphate and nitrate buffer solution and the electrochemical properties of surfaces was investigated in probe media and sulfuric acid. This fabrication method was simple, facile and controllable, without any seed, template or surfactant.  相似文献   

5.
The electropolymerization of trans-[RuCl2(vpy)4] (vpy=4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) technique, and Raman spectroscopy. Cyclic voltammetry of the monomer at a microelectrode shows the typical Ru(III/II) and Ru(IV/III) waves, together with the vinyl reduction waves at −1.5 and −2.45 V and adsorption wave at −0.8 V. Electrodeposition on EQCM technique performed under potential cycling between −0.9 and −2.0 V revealed that the polymerization proceeded well in advance of the vinyl reduction waves. At potentials more positive than −0.9 V, soluble oligomers were deposited irreversibly on the electrode during the oxidative sweep. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. In contrast, potentiostatic growth of the polymer at −1.6 V was slower because the oligomeric material was lost completely from the electrode. Unreacted vinyl groups were detected by in situ Raman spectroscopy for films grown at −0.7, −0.9, and −1.6 V but were absent when the polymerization was carried out at −2.9 V vs Ag/Ag+.  相似文献   

6.
Composite electrodes were prepared from chemical vapor deposition grown carbon nanofibers consisting predominantly of ca. 100 nm diameter fibers. A hydrophobic sol–gel matrix based on a methyl-trimethoxysilane precursor was employed and composites formed with carbon nanofiber or carbon nanofiber—carbon particle mixtures (carbon ceramic electrode). Scanning electron microscopy images and electrochemical measurements show that the composite materials exhibit high surface area with some degree of electrolyte solution penetration into the electrode. These electrodes were modified with redox probe solution in 2-nitrophenyloctylether. A second type of composite electrode was prepared by simple pasting of carbon nanofibers and the same solution (carbon paste electrode). For both types of electrodes it is shown that high surface area carbon nanofibers dominate the electrode process and enhance voltammetric currents for the transfer of anions at liquid|liquid phase boundaries presumably by extending the triple-phase boundary. Both anion insertion and cation expulsion processes were observed driven by the electro-oxidation of decamethylferrocene within the organic phase. A stronger current response is observed for the more hydrophobic anions like ClO4 or PF6 when compared to that for the more hydrophilic anions like F and SO42−. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005  相似文献   

7.
In order to enhance the performance of a solid-state MnO2-metal hydride battery using H3PMo12O40 · 20H2O as an electrolyte, a moderate amount of the electrolyte was added to both positive and negative electrodes. The high rate characteristics of the battery were improved significantly by optimizing the electrolyte content in the electrodes; the resulting battery was able to operate over 140 cycles, even at a current density of 20 mA/g alloy, which is large enough for the batteries using inorganic solid electrolytes, and keep the discharge efficiency about 90%. The improvement of battery performance appears to be caused by an increase in electrode-electrolyte interface area. The AC impedance analyses revealed that the resistance of interface is decreased by the addition of a suitable amount of the electrolyte, suggesting an increase in the interface area.  相似文献   

8.
The oxidative and reductive electrochemistry of the three isomeric nitroanilines has been studied in neutral (0.1 mol L−1 KClO4) and acidic (0.1 mol L−1 HClO4) aqueous electrolyte solutions by cyclic voltammetry and surface enhanced Raman spectroscopy (SERS). The cyclic voltammograms recorded for o- and p-nitroanilines with a gold electrode in acidic solution, scanning toward negative potentials, revealed formation of phenylenediamine not observed in neutral solution. Similar behavior of nitroanilines and phenylenediamines was observed on gold and platinum electrodes. An oxygen–gold adsorbate stretching mode was detected between 400 and 430 cm−1 in the SER-spectra of the three isomeric nitroanilines in both electrolyte solutions at positive electrode potentials, implying perpendicular adsorption via the nitro group.  相似文献   

9.
SiO2/Sb2O3 (SiSb), having a specific surface area, S BET, of 788 m2 g−1, an average pore diameter of 1.9 nm and 4.7 wt% of Sb, was prepared by the sol-gel processing method. Meldola's blue (MeB), methylene blue (MB) and toluidine blue (TB) were immobilized on SiSb by an ion exchange reaction. The amounts of the dyes bonded to the substrate surface were 12.49, 14.26 and 22.78 μmol g−1 for MeB, MB and TB, respectively. These materials were used to modify carbon paste electrodes. The midpoint potentials (E m) of the immobilized dyes were −0.059, −0.17 and −0.18 V vs. SCE for SiSb/MeB, SiSb/MB and SiSb/TB modified carbon paste electrodes, respectively. A solution pH between 3 and 7 practically did not affect the midpoint potential of the immobilized dyes. The electrodes presented reproducible responses and were chemically stable under various oxidation-reduction cycles. Among the immobilized dyes, MeB was the most efficient to mediate the electron transfer for NADH oxidation in aqueous solution at pH 7. In this case, amperometric detection of NADH at an applied potential of 0 mV vs. SCE gives linear responses over the concentration range of 0.1–0.6 mmol L−1, with a detection limit of 7 μmol L−1.  相似文献   

10.
The electropolymerisation of N-benzylaniline (NBA) at transparent ITO glass electrodes was investigated with in situ UV-visible spectroelectrochemistry. An intermediate was found to be generated during electrolysis as the precursor of poly(N-benzylaniline) (PNBA). The intermediate, which shows an absorbance band at λ = 460 nm, is able to react spontaneously with NBA, forming a polymeric end product, which is deposited on the electrode surface. UV-Vis spectra were obtained with PNBA-modified electrodes at various electrode potentials. It was shown that the colouration of the PNBA film after a positive-going potential step proceeds ca. 5 times slower than its discolouration after the reverse negative-going potential step. Anodic degradation of PNBA film was shown to proceed when holding the electrode at a sufficiently high positive potential. A linear dependence between the first-order degradation rate constant (k/s−1) and electrode potential (E/V) was found in the potential range of E RHE = +0.8 to +1.1 V: log k = a + bE, where a = −8.75 and b = 5.45 are empirical coefficients. In the whole spectral range investigated, the degradation of PNBA was found to proceed faster as compared to that of polyaniline (for polyaniline, coefficients a = −12.7 and b = 8.96 were obtained in the potential range of E RHE = +0.85 to +1.1 V). The electrooxidation of hydroquinone, as well as the electroreduction of benzoquinone, were shown to proceed at PNBA-modified electrodes. In these processes, PNBA was shown to play the role of an electron mediator between the ITO electrode and solution phase redox species. Received: 8 January 1999 / Accepted: 27 January 1999  相似文献   

11.
In this work, 3-methylthiophene (MeT) was electrochemically incorporated with nano- and mesoporous TiO2 films to form poly(3-methylthiophene) (PMeT)/TiO2 nanocomposite electrochromic electrodes. TiO2 films, which were previously coated on the ITO glass sheets through a well-established technique, were introduced to enhance the adhesion of the polymers to the substrates and thus increase the long-term stability of the devices. With this effort, the nanocomposite electrodes were found to retain up to 60% of their optical response after 3,500 deep and double potential steps and retain up to 50% of their electroactivity after 104 same steps, exhibiting enhanced long-term stability. Switching time and the maximum optical contrast (ΔT%) of the nanocomposite electrodes were found to be 0.6 s and 45%, respectively. Moreover, our work showed that electrochemically incorporating conductive polymers (CPs) with TiO2 mesoporous films was an effective method to form high-quality CP/TiO2 nanocomposite electrodes, which can be used widely in battery cathodes, photovoltaic cells, photocatalytic reaction, and photoelectrochromic cells and were supposed to enhance their performances.  相似文献   

12.
In this study the application of home-made unmodified (GC) and bulk modified boron doped glassy carbon (GCB) electrodes for the voltammetric determination of the linuron was investigated. The electrodes were synthesized with a moderate temperature treatment (1000°C). Obtained results were compared with the electrochemical determination of the linuron using a commercial glassy carbon electrode (GC-Metrohm). The peak potential (E p ) of linuron oxidation in 0.1 mol dm−3 H2SO4 as electrolyte was similar for all applied electrodes: 1.31, 1.34 and 1.28 V for GCB, GC and GC-Metrohm electrodes, respectively. Potential of linuron oxidation and current density depend on the pH of supporting electrolyte. Applying GCB and GC-Metrohm electrodes the most intensive electrochemical response for linuron was obtained in strongly acidic solution (0.1 mol dm−3 H2SO4). Applying the boron doped glassy carbon electrode the broadest linear range (0.005–0.1 μmol cm−3) for the linuron determination was obtained. The results of voltammetric determination of the linuron in spiked water samples showed good correlation between added and found amounts of linuron and also are in good agreement with the results obtained by HPLC-UV method. This appears to be the first application of a boron doped glassy carbon electrode for voltammetric determination of the environmental important compounds.   相似文献   

13.
We have studied the electrocatalytic activity of RuO2-PVC film electrodes, fabricated using RuO2 powders prepared at five different temperatures, viz., 300, 400, 500, 600 and 700°C, for the oxidation of glucose in high alkaline media, 1 to 3 M NaOH. The RuO2-PVC film electrodes have been first characterized in 1 to 3 M NaOH solution by cyclic voltammetry (CV) and rotating disc electrode (RDE) techniques in a wide potential range −1,100 to 450 mV (SCE), and three redox pairs representing Ru(IV)/Ru(III), Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI) transitions have been identified. The voltammetric peaks at low sweep rates have been analyzed using surface activity theory formulated for interacting electroactive adsorption sites, and interaction terms have been evaluated. The total voltammetric surface charges have been analyzed as per Trassatti’s formalism with respect to their dependence on potential sweep rate, and charges associated with less accessible and more accessible surface sites have been calculated. For glucose oxidation, the results have indicated that RuO2 (700°C)-PVC electrode shows two oxidation peaks in contrast to RuO2 (300°C)-PVC electrode. Also, RuO2 (700°C)-PVC electrode exhibits higher intrinsic electrocatalytic activity than the 300°C electrode, although the former possesses lower electrochemically active surface area. Additionally, kinetic analyses made from RDE results with reference to Michealis–Menten (MM) enzyme catalysis has shown that RuO2 (700°C) electrode possesses extended glucose-sensing range in terms of MM kinetic constant, K M , compared to other electrodes. Possible reasons for such differences in the behavior of the electrodes of different temperatures towards glucose oxidation are identified from studies on oxidation of glucose in solutions of different pH, oxidation of different glucose derivatives, and also from physicochemical results from BET, XRD, SEM, DTGA, XPS analysis of RuO2 powder samples.  相似文献   

14.
Positive electrode with uniform lead dioxide nanostructures directly synthesized by cyclic voltammetry (CV) method on the lead substrate in 1 M sulfuric acid solution including different concentration of barium sulfate. The effect of potential scan rate, sulfuric acid and barium sulfate concentration were studied on the morphology and particle size of lead dioxide using scanning electron microscopy (SEM) and X-ray diffraction techniques (XRD). The effect of barium sulfate was studied on the CV parameters including anodic peak current (I pa), cathodic peak current (I pc), anodic peak potential (E pa) and cathodic peak potential (E pc) during synthesis process. Finally, the effect of barium sulfate on the discharge capacity and cycle life of nanostructured positive electrodes and commercial positive plates was investigated. Both CV and battery test results showed that barium sulfate with concentration of 1 × 10−5 M can be used as suitable additive for positive paste of lead-acid batteries.  相似文献   

15.
Oxygen reduction on well-defined single-crystal electrodes in different basic and neutral media has been studied using the impinging jet system. The results obtained with this system in 0.1 M NaOH are comparable to those reported in the literature for rotating disk electrodes, indicating that the impinging jet system behaves as a system in which the thickness of the diffusion layer is stationary. The activity of the Au(100) electrode is considerably higher than the rest of the basal planes in all media and yields water when E>–0.2 V and hydrogen peroxide for E<–0.2 V on the SHE scale. For Au(111) and Au(110) the activity of the electrode is much smaller and the final product is always hydrogen peroxide. The transition between both mechanisms for the Au(100) is, essentially, independent of the solution pH. In acid media the final product is always hydrogen peroxide for all the electrodes studied. The differences between the activities of the electrodes have been explained in the light of the different adsorption properties of the surfaces in relation to HO2 . In the case of the Au(100) electrode, the existence of a negative charge density on the metal inhibits further reduction of HO2 .Dedicated to Prof. Dr. Wolf Vielstich on the occasion of his 80th birthday in recognition of his numerous contributions to interfacial electrochemistry  相似文献   

16.
A new type of carbon paste electrode (CPE) was made using ketotifen fumarate (C23H23NO5S; an antiasthmatic/antianaphylactic drug) and hexacyanoferrate. This electrode was constructed using an acidic solution of ketotifen fumarate and potassium hexacyanoferrate. For this purpose, ketotifen fumarate was dissolved in acidic solution (pH 1) and hexacyanoferrate was added by agitation, resulting in ketotifen–hexacyanoferrate (Ket–HCF) precipitate. The obtained precipitate was separated and introduced into carbon paste. The electrochemical behavior of Ket–HCF CPE was studied by cyclic voltammetry. A modified electrode shows one pair of peaks with surface-confined characteristics, with a 0.1-M phosphate buffer as supporting electrolyte. The effects of pH, alkali metal cations, and anions of supporting electrolytes on the electrochemical characteristics of modified electrodes were studied. The diffusion coefficients of hydrated K+ in film (D), the transfer coefficient (α), and the transfer rate constant for electrons (k s) were determined.  相似文献   

17.
采用磁悬浮感应熔炼法制备了组分为LaY_2Ni_(9.7)Mn_(0.5)Al_(0.3)的合金,在不同温度(1 073~1 373 K)下对合金进行热处理,利用X射线衍射法(XRD)、电子探针(EPMA)和电化学性能测试等方法,系统地研究了热处理温度对合金相结构和电化学性能的影响。结果表明,热处理可以显著提高合金的相均匀度,随着热处理温度的升高合金中的主相Ce_2Ni_7相先增加后减少。电化学研究表明,合金电极的最大放电容量、倍率性能和循环稳定性随着热处理温度的升高均呈现先升高后降低的趋势,与Ce_2Ni_7相含量的变化一致。电化学压力-组成-温度(P-C-T)测试表明,合金具有2个放氢平台,且随着热处理温度的升高合金的放氢坪台压增加。当热处理温度为1 273 K时,合金的Ce_2Ni_7相含量最高为86.53%(w/w),电化学性能最佳,最大放电容量为386.80 mAh·g~(-1)(60mA·g~(-1)),在电流密度为900 mA·g~(-1)时的高倍率性能HRD_(900)=89.45%,循环300周后的容量保持率S_(300)=72.18%(300 mA·g~(-1))。  相似文献   

18.
New poly (vinylidenefluoride-co-hexafluoro propylene) (PVDF-HFP)/CeO2-based microcomposite porous polymer membranes (MCPPM) and nanocomposite porous polymer membranes (NCPPM) were prepared by phase inversion technique using N-methyl 2-pyrrolidone (NMP) as a solvent and deionized water as a nonsolvent. Phase inversion occurred on the MCPPM/NCPPM when it is treated by deionized water (nonsolvent). Microcomposite porous polymer electrolytes (MCPPE) and nanocomposite porous polymer electrolytes (NCPPE) were obtained from their composite porous polymer membranes when immersed in 1.0 M LiClO4 in a mixture of ethylene carbonate/dimethyl carbonate (EC/DMC) (v/v = 1:1) electrolyte solution. The structure and porous morphology of both composite porous polymer membranes was examined by scanning electron microscope (SEM) analysis. Thermal behavior of both MCPPM/NCPPM was investigated from DSC analysis. Optimized filler (8 wt% CeO2) added to the NCPPM increases the porosity (72%) than MCPPM (59%). The results showed that the NCPPE has high electrolyte solution uptake (150%) and maximum ionic conductivity value of 2.47 × 10−3 S cm−1 at room temperature. The NCPPE (8 wt% CeO2) between the lithium metal electrodes were found to have low interfacial resistance (760 Ω cm2) and wide electrochemical stability up to 4.7 V (vs Li/Li+) investigated by impedance spectra and linear sweep voltammetry (LSV), respectively. A prototype battery, which consists of NCPPE between the graphite anode and LiCoO2 cathode, proves good cycling performance at a discharge rate of C/2 for Li-ion polymer batteries.  相似文献   

19.
Poly(4-vinylpyridine) (PVP)-based anion exchange polymers are not studied as much as cation exchange polymers Nafion and Eastman Kodak AQ for electroanalytical applications. Similarly, octacyanomolybdate [Mo(CN)8 4−] has not been studied much as a redox mediator. This communication presents results from examinations of the behaviour of Mo(CN)8 4−-doped PVP ionomer film electrode to highlight the opportunities for realization of the application of this composite electrode for l-ascorbic acid (AH2) estimation via electrocatalytic mediation in acidic medium. The modified electrodes were characterized by cyclic voltammetry and rotating disc electrode voltammetry. PVP coatings possess strong anion-binding capacity for Mo(CN)8 4− mediator with an extraction coefficient of 990, and electrostatically cross-linked PVP films offer insignificant resistance to permeation of AH2, facilitating a cross-exchange reaction between the substrate and the mediator in the entire film volume. They show effective electrocatalytic oxidation of AH2, with the oxidation potential of AH2 decreased by ∼200 mV in overpotential compared to that at bare electrode. Mo(CN)8 4−/PVP composite electrode does not respond to the more common interferents of l-ascorbic acid estimation even at high positive potentials. These and several other attractive potentialities of the modified electrode are demonstrated by direct determination of AH2 in a commercial vitamin C tablet without any special treatment, with the value closely agreeing (±0.75%) with the reference method.  相似文献   

20.
The electrocatalytic activity of a Prussian blue (PB) film on the aluminum electrode by taking advantage of the metallic palladium characteristic as an electron-transfer bridge (PB/Pd–Al) for electrooxidation of 2-methyl-3-hydroxy-4,5-bis (hydroxyl–methyl) pyridine (pyridoxine) is described. The catalytic activity of PB was explored in terms of FeIII [FeIII (CN)6]/FeIII [FeII (CN)6]1− system. The best mediated oxidation of pyridoxine (PN) on the PB/Pd–Al-modified electrode was achieved in 0.5 M KNO3 + 0.2 M potassium acetate of pH 6 at scan rate of 20 mV s−1. The mechanism and kinetics of the catalytic oxidation reaction of PN were monitored by cyclic voltammetry and chronoamperometry. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The charge transfer-rate limiting reaction step is found to be a one-electron abstraction, whereas a two-electron charge transfer reaction is the overall oxidation reaction of PN by forming pyridoxal. The value of α, k, and D are 0.5, 1.2 × 102 M−1 s−1, and 1.4 × 10−5 cm2 s−1, respectively. Further examination of the modified electrodes shows that the modifying layers (PB) on the Pd–Al substrate have reproducible behavior and a high level of stability after posing it in the electrolyte or Pyridoxine solutions for a long time.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

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