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The reaction of electroreduction of platinum(II) aquachloride complexes on a negatively charged dropping mercury electrode is used to determine specific features of interpretation of experimental data in the case of parallel conversion of several forms of a reactant, connected with the manner of introducing a correction for the concentration polarization. The difference in the charges of species undergoing simultaneous reduction gives rise to ambiguity when analyzing kinetic data on the dependence of current on the supporting-electrolyte concentration at constant electrode charge. A new self-consistent technique for deducing model parameters (ratio between reactant discharge rate constants) is proposed. 相似文献
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A critical analysis shows that the approach to the estimation of the charge transfer in the process of adsorption at the electrode/solution interface used by Vetter and Schultze in the general case is not justified without introduction of non-thermodynamic models. This approach can prove useful in the investigation of the electric double layer within the limits of applicability of Grahame's model. A number of cases can however be cited where the approach of Schultze and Vetter is inapplicable. The conclusions of Schultze and Vetter regarding the adsorption of hydrogen at platinum are apparently based on some misunderstanding. In this case the thermodynamic approach6, 23 should be used.It would be more correct to call the quantity γ “the formal coefficient of charge transfer”, rather than “the electrosorption valency”. 相似文献
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T. Ya. Safonova N. S. Gulyukina Yu. V. Novakovskaya E. A. Astaf'ev G. N. Bondarenko O. A. Petrii G. A. Tsirlina I. P. Beletskaya 《Russian Journal of Electrochemistry》2002,38(5):457-466
The conditions for electrochemical hydrogenation and anodic oxidation of -phenylvinylphosphonic acid and its 4-chloro- and 4-methyl-substituted derivatives on palladized platinum electrodes in aqueous sulfuric-acid solutions are found. It is shown that, in the system under study, the products of strong chemisorption are not the intermediates of the electrocatalytic hydrogenation. The reactant molecules are modeled by quantum-chemical methods in terms of the restricted Hartree–Fock approximation. The calculated charge distributions in reactant molecules are used for estimating the electrostatic components of works of approach and the orientation distributions in the reaction layer. 相似文献
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N. V. Smirnova N. S. Gulyukina E. A. Astaf'ev O. A. Petrii G. A. Tsirlina I. P. Beletskaya 《Russian Journal of Electrochemistry》2002,38(6):626-632
A general characteristic of cathodic reduction of -phenylvinylphosphonic acid and its methyl- and chloro-parasubstituted derivatives on Pt/Pt, Pd/Pt, and Pd/Pt modified with Cd and Cu adatoms, is given. At effective pressures of about 103–104 Pa the processes occur at high rates and at some potentials are limited by the reactant diffusion from the bulk solution. In the presence of Cd and Cu adatoms two reduction waves (presumably, single-electron) may be isolated, i.e. the hampering by adatoms is more pronounced for a second successive stage of the process. At low effective hydrogen pressures the hydrogenation rate is higher on Pd electrodes, which possess a larger sorption capacity. Potential intervals where the reduction of substituted reactants may be complicated by destruction, are found. It is shown that -phenylvinylphosphonic acid undergoes a complete reduction with a current efficiency of 100% in both hydrochloric- and sulfuric-acid solutions. Conditions where the reduction of -(4-chlorophenyl)vinylphosphonic acid proceeds largely without destruction are found. Prospects for use of electrochemical reduction as a preparative method of a selective production of -arylethylphosphonic acids are considered. 相似文献
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Russian Journal of Electrochemistry - 相似文献
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Kudryavtsev V. N. Gamburg Yu. D. Petrii O. A. Grafov B. M. 《Russian Journal of Electrochemistry》2003,39(3):331-332
Russian Journal of Electrochemistry - 相似文献
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Pavel A. Zagrebin Galina A. Tsirlina Renat R. Nazmutdinov Oleg A. Petrii Michael Probst 《Journal of Solid State Electrochemistry》2006,10(3):157-167
The advantages of corrected Marcus plots as compared to the more traditional corrected Tafel plots are discussed and illustrated
by the treatment of experimental data. The procedures are proposed to avoid the uncertainties of EDL correction and to estimate
the reliable values of transmission coefficient and total reorganization energy. Special emphasis is placed on the diagnostics
of activationless reactions in frames of the same method.
Dedicated to Professor M.A. Vorotyntsev on the occasion of his 60th birhtday.
相似文献
Galina A. TsirlinaEmail: |
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Oleg A. Petrii 《Journal of Solid State Electrochemistry》2008,12(5):609-642
Three periods of Pt–Ru research are considered step-by-step: the initial period after discovery (1963–1970); observation and
classification of basic tendencies (like the effects of composition, segregation, structural features on the activity; up
to 1990); nanostructural studies and molecular level consideration of electrocatalytic phenomena in combination with advanced
applied studies of materials, mechanistic, and applied aspects (after 1990). The main idea of this review is to balance various
aspects of Pt–Ru electrochemistry related to material science and electrocatalysis as well as to remember the early basic
results being of importance for future understanding of Pt–Ru functional properties.
Dedicated to Professor Teresa Iwasita, as a token of her remarkable contribution to electrocatalysis.
相似文献
Oleg A. PetriiEmail: |