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1.
The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible. 相似文献
2.
The kinetics of reactions occurring at the gas-exposed surfaces of charged mixed ionic electronic conductors (MIECs) are examined
from theoretical first principles. Analysis based on the classical electrochemical potential-transition state theory model
reveals that the nature of the reactions is electrochemical in general. However, the influence of the surface potential on
the reaction rate is opposite for adsorption and incorporation reactions. Two-dimensional finite volume models of an MIEC
as working electrode in a half-cell configuration are presented. The results for a simple, two-step reduction process show
that the effect of the surface potential on the rate of reactions is minimal for incorporation-limited reactions but more
influential for adsorption-limited reactions.
An erratum to this article is available at . 相似文献
3.
An exact method based on Green's equation is used to find the diffusion-controlled faradaic current for certain electrode geometries that incorporate edges and vertices. Thereby the magnitudes of the time-independent current density associated with angled electrode/electrode and electrode/insulator junctions are calculated. As well, the square-root-of-time-dependent currents associated with vertices, receive attention. These terms extend to longer times, the Cottrell formulation appropriate for short times. Though most of the problems solved here have been tackled previously, the novel Green function approach is shown to be straightforward and intuitive. 相似文献
4.
5.
Polymer electrolyte systems were prepared for the first time by dissolution of amidomagnesium chlorides in poly(ethylene oxide),
(PEO). For the preparation, solutions of (hexamethyldisilylamido)magnesium chloride, (dimethylpyrrolyl)magnesium chloride,
(diisopropylamido)magnesium chloride, piperidinomagnesium chloride and morpholinomagnesium chloride were chosen. The composition
of these polymer electrolyte systems corresponds to the general formula R2NMgCl·P(EO)n·THF. Most work has been done with the system (hexamethyldisilylamido)magnesium chloride in PEO, (Me3Si)2NMgCl·P(EO)n·THF, with n= 3, 4, 5, or 7. The electrolytes have a soft rubber-like consistency. At 30 °C, electrical conductivities of 10−6–10−5 S/cm were found. The conductivities were measured in the temperature range 20–60 °C. Within this temperature range a linear
dependence of the logarithms of the conductivity on the inverse temperature was found and activation energies for the conducting
process of 30–60 kJ/mol were calculated. Using those polymer electrolytes with a high content of the amidomagnesium compound,
a reversible magnesium deposition takes place by cathodic reduction at potentials below −1.9 V vs. a Ag/AgCl reference electrode.
These polymer electrolytes were found to be stable against oxidation up to about −0.3 V vs. Ag/AgCl.
Electronic Publication 相似文献
6.
There is a need to develop reliable portable analytical systems for on-site and real-time biomonitoring of lead (Pb) from both occupational and environmental exposures. Saliva is an appealing matrix since it is easily obtainable, and therefore a potential substitute for blood due to existing reasonably good correlation between Pb levels in blood and saliva. The microanalytical system is based on flow-injection/stripping voltammetry with a wall-jet (flow-onto) microelectrochemical cell. Samples that contain as little as 1% saliva can cause electrode fouling, resulting in significantly reduced responsiveness and irreproducible quantitations. In addition, incomplete Pb release from salivary protein can also yield a lower Pb response than expected. This paper evaluates the extent of in vitro Pb-protein binding and the optimal pretreatment for releasing Pb from the saliva samples. Even in 50% by volume of rat saliva, the electrode fouling was not observed, due to the appropriate sample pretreatment and the constant flow of the sample and acidic carrier that prevented passivation by the protein. The system offered a linear response over a low Pb range of 1-10 ppb, low detection limit of 1 ppb, excellent reproducibility, and reliability. It also yielded the same Pb concentrations in unknown samples as did the ICP-MS. These encouraging results suggest that the microanalytical system represents an important analytical advancement for real-time non-invasive biomonitoring of Pb. 相似文献
7.
Nanometric vanadium antimonate, VSbO4, was prepared by mechanical milling from Sb2O3 and V2O5 and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Mossbaüer spectroscopy (MS) and X-ray photoelectron spectroscopy (XPS) techniques. Its reactivity towards lithium was examined by testing Li/VSbO4 cells under galvanostatic and potentiostatic regimes. The amount of Li inserted was found to be consistent with a two-step process involving the reactions (i) VSbO4+8 Li→Sb+V+4 Li2O and (ii) Sb+3 Li→Li3Sb, the former being virtually irreversible and the latter reversible as suggested by the shape of the anodic and cathodic curves. Ex situ XPS measurements of the discharged and charged electrode provided direct evidence of the formation of alloyed Sb and confirmed the results of the potentiostatic curves regarding the irreversible or reversible character of the previous reactions. The Li/VSbO4 cell exhibited acceptable electrochemical performance, which surpassed that of other Sb-based compounds as the likely result of the formation of V and its associated enhanced electrode conductivity. 相似文献
8.
Michael P Bokoch 《Analytica chimica acta》2004,519(1):47-55
Cholesterol oxidase is immobilized in electrode-supported lipid bilayer membranes. Platinum electrodes are initially modified with a self-assembled monolayer of thiolipid. A vesicle fusion method is used to deposit an outer leaflet of phospholipids onto the thiolipid monolayer forming a thiolipid/lipid bilayer membrane on the electrode surface. Cholesterol oxidase spontaneously inserts into the electrode-supported lipid bilayer membrane from solution and is consequently immobilized to the electrode surface. Cholesterol partitions into the membrane from buffer solutions containing cyclodextrin. Cholesterol oxidase catalyzes the oxidation of cholesterol by molecular oxygen, forming hydrogen peroxide as a product. Amperometric detection of hydrogen peroxide for continuous solution flow experiments are presented, where flow was alternated between cholesterol solution and buffer containing no cholesterol. Steady-state anodic currents were observed during exposures of cholesterol solutions ranging in concentration from 10 to 1000 μM. These data are consistent with the Michaelis-Menten kinetic model for oxidation of cholesterol as catalyzed by cholesterol oxidase immobilized in the lipid bilayer membrane. The cholesterol detection limit is below 1 μM for cholesterol solution prepared in buffered cyclodextrin. The response of the electrodes to low density lipoprotein solutions is increased upon addition of cyclodextrin. Evidence for adsorption of low density lipoprotein to the electrode surface is presented. 相似文献
9.
E.?V.?TsipisEmail author V.?V.?Kharton I.?A.?Bashmakov E.?N.?Naumovich J.?R.?Frade 《Journal of Solid State Electrochemistry》2004,8(9):674-680
Developments of intermediate-temperature solid oxide fuel cells (IT SOFCs) require novel anode materials with a high electrochemical activity at 800–1070 K. The polarization of cermet anodes, made of nickel, ceria and yttria-stabilized zirconia (YSZ) and applied onto a YSZ solid electrolyte, can be significantly reduced by catalytically active ceria additions, the relative role of which increases with decreasing temperature. Further improvement is observed when using Ce0.8Gd0.2O2–
(CGO) having a high oxygen ionic conductivity instead of undoped ceria, owing to enlargement of the electrochemical reaction zone. Nanocrystalline CGO powders with grain sizes of 8–35 nm were thus synthesized via the cellulose-precursor technique and introduced into Ni–CGO–YSZ cermets, and tested in contact with a (La0.9Sr0.1)0.98Ga0.8Mg0.2O3–
(LSGM) electrolyte at 873–1073 K. The results showed that the anode performance can be enhanced by additional surface activation, in particular by impregnation with a Ce-containing solution, and also by incorporation of YSZ, which probably acts as a cermet-stabilizing component. The overpotential of the surface-modified Ni–CGO (25 wt%–75 wt%) anode in a 10% H2/90% N2 atmosphere was approximately 110 mV at 1073 K with a current density of 200 mA/cm2.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
10.
J. Tolchard 《Journal of solid state chemistry》2007,180(10):2808-2815
The chemical and physical compatibility of SrCeO3 is investigated with respect to LaMO3 (M=Mn, Fe, Co) and La2−xSrxNiO4 (x=0, 0.8), via the reaction of fine-grained powder compacts and solid-state diffusion couples. Compositions were chosen so as to give predictive insight into possible candidate materials for all-oxide electrochemical devices. Results show the primary reaction in these systems to be the dissolution of SrO from SrCeO3 into the LaMO3/La2−xSrxNiO4, and corresponding formation of La-doped CeO2. Reaction kinetics are observed to be relatively fast, with element profiles suggesting the diffusion of Sr2+ in ceria to be surprisingly rapid. It is demonstrated that perovskite starting materials represent poor candidates for use with SrCeO3, reacting completely to form Ruddlesden-Popper/K2NiF4 type oxides. Reaction with La2NiO4 is less pronounced, and formation of secondary phases suppressed for the composition La1.2Sr0.8NiO4. It is thus concluded that Ruddlesden-Popper type oxides represent good candidate materials for use with a SrCeO3-based electrolytes when doped with appropriate levels of Sr. 相似文献