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Molecules ; 27(17)2022 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-36080404


A power source based on the current-generating reaction of aqueous chlorate-to-chloride reduction by molecular hydrogen would provide as much as 1150 Wh per 1 L of reagent storage (for a combination of 700 atm compressed hydrogen and saturated aqueous solution of lithium chlorate) at room temperature, but direct electroreduction of chlorate only proceeds with unacceptably high overvoltages, even for the most catalytically active electrodes. In the present study, we experimentally demonstrated that this process can be performed via redox-mediator catalysis by intermediate products of chlorate reduction, owing to their participation in homogeneous com- and disproportionation reactions. A series of current-voltage and discharge characteristics were measured for hydrogen-chlorate membrane-electrode assembly (MEA) cells at various concentrations of chlorate and sulfuric acid under operando spectrophotometric monitoring of the electrolyte composition during the discharge. We established that chlorine dioxide (ClO2) is the key intermediate product; its fraction in the electrolyte solution increases progressively, up to its maximum, equal to 0.4-0.6 of the initial amount of chlorate anions, whereas the ClO2 amount decreases gradually to a zero value in the later stage. In most discharge experiments, the Faradaic yield exceeded 90% (maximal value: 99%), providing approximately 48% chemical energy storage-to-electricity conversion efficiency at maximal power of the discharge (max value: 402 mW/cm2). These results support prospect of a hydrogen-chlorate flow current generator as a highly specific energy-capacity source for airless media.

Chempluschem ; 85(8): 1919-1927, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32856795


A great deal of research has been dedicated to improving the performance of vanadium redox flow battery (VRFB). In this work, we propose the design of a cell for testing membrane electrode assembly of VRFB, which enables the optimization of the flow field, conditions of charge-discharge tests, and the nature of components (electrodes, membrane) with minimal time and material expenses. The essence of the proposed cell is that the system of channels distributing the electrolyte is made by cutting shaped holes in the sheets of graphite foil (GF). This manner allows easy modification of the flow field configurations. Polarization curves for serpentine, interdigitated, and flow-through systems were measured according to procedures used in such studies. Cell with GF plates being tested with vanadium-sulfuric acid electrolyte, outperforms the cell with conventional graphite plates with the same parameters of the flow field. It demonstrates 734 mW cm-2 of peak power density at SOC 50 and 84.3 % of energy efficiency at 84.5 % of electrolyte utilization under galvanostatic charge/discharge cycling with 75 mA cm-2 .

Phys Chem Chem Phys ; 12(35): 10525-35, 2010 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-20614058


Electrochemical behavior of Pt and Au electrodes in acetonitrile solutions at different concentration ratios of Cl(-) and Ag(+) ions was studied by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The composition of the mixed silver chloride solutions, i.e. the amount of each component of the system (solid AgCl and solute species: Ag(+), Cl(-), AgCl(2)(-)), is governed by the solubility product of AgCl and the stability constant of AgCl(2)(-)complex and depends strongly on the ratio of the total concentrations of chloride and silver ions. In this work we analyze in detail the influence of the Cl(-)/Ag(+) concentration ratio on the value of equilibrium electrode potential and the shape of cyclic voltammograms. We explain the complicated shapes of the experimental curves observed at different concentration ranges, propose the mechanisms of the processes occurring at the electrode and substantiate them by EQCM data.

J Phys Chem B ; 113(4): 1085-99, 2009 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-19128051


Several earlier studies of the electrochemical oxidation of ferrocene (Fc) in room-temperature ionic liquids revealed an essentially nonlinear dependence of the oxidation current on the Fc concentration in its relatively dilute solutions, with its formally calculated diffusion coefficient strongly increasing with the concentration. Since no plausible mechanism leading to this very unusual finding had been proposed, our study of Fc solutions in 1-butyl-3-methylimidazolium triflimide, [BMIM][NTf(2)], was performed to verify whether the above observation originated from an incorrect determination of the dissolved Fc concentration. Our observations have demonstrated that reliable control of the Fc concentration in solution is complicated by factors such as the low amount of Fc used to prepare small-volume solutions or the great difficulty to dissolve completely a solid powder in a solvent with an extremely high viscosity. An unexpected additional complication is related to a sufficiently high volatility of Fc which manifests itself even at room temperature and especially at elevated temperatures or/and in the course of vacuum treatment of its solutions or its solid powder. Parallel measurements of electrochemical responses and UV-visible spectra for several series of Fc solutions of various concentrations (prepared with the use of different procedures) have shown a perfect parallelism between the peak current and the intensity of the absorption band in the range of 360-550 nm, leading us to the conclusion of a linear relationship between the oxidation current and the molecularly dissolved Fc concentration. The relations of these measured characteristics with the estimated Fc concentration in these solutions have demonstrated a much greater dispersion (attributed to the difficulty of a precise measurement of the latter) but without a significant deviation from the linearity in general. This finding has allowed us to estimate the diffusion coefficient of this species: D = (1.7 +/- 0.2) x 10(-7) cm(2)/s. The extinction coefficients for the maximum of the absorption band (at 440 nm) of Fc have been compared for a series of solvents: [BMIM][NTf(2)], acetonitrile, THF, heptane, CH(2)Cl(2), ethanol, and toluene. A simple method to estimate reliably the concentration of solute Fc in ionic liquids based on spectroscopic measurements has been proposed, owing to the proximity of Fc absorption properties for a great variety of solvents.

Adv Colloid Interface Sci ; 139(1-2): 97-149, 2008 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-18358450


The paper gives a review of publications on polymers with conjugated matrices (PPy, PTh, PAni, hydrocarbon or mixed chains...) which incorporate metallocene complexes (Fe, Ru, Co; Ni, Ti, Zr, Ta) with two cyclopentadienyl ligands (Cp) and their derivatives, in particular with methylated cyclopentadienyl rings (Cp*), as well as hemi-metallocene complexes (Fe, Ru, Co, Mn), as pendant groups or inside the principal chain (part B). The information on related short-chain systems, monomers and oligomers, is also included. In part A, a brief overview of various conjugated polymer materials is presented, with their classification in accordance with the conductivity mechanism (ionic, electronic or mixed conductors) or with the structural type (linear-chain organic or mixed polymers, derivatization, metallopolymers, multi-dimensional structures, alternating and block copolymers with organic or mixed units, hybrid materials with a mixture of conjugated and inert polymers, polymers inside a solid matrix, conjugated polymers with incorporated nanoelements of transition metals, carbon, semiconductors etc.