Electroreduction of Bi(III) Ions at a Cyclically Renewable Liquid Silver Amalgam Film Electrode in the Presence of Methionine

The catalytic influence of methionine (Mt) on the electroreduction of Bi(III) ions on the novel, cyclically renewable liquid silver amalgam film electrode (R–AgLAFE) in a non-complexing electrolyte solution was examined. The presence of methionine leads to a multistep reaction mechanism, where the transfer of the first electron is the rate limiting step, which is the subject of catalytic augmentation. The catalytic activity of methionine is a consequence of its ability to remove water molecules from the bismuth ion coordination sphere, as well as to form active complexes on the electrode surface, facilitating the electron transfer process.     

Catalytic activity of thiourea and its selected derivatives on electroreduction of In(III) in chlorates(VII)

It was found that thiourea, N-methylthiourea, N,N′-dimethylthiourea and N-allylthiourea accelerate the electroreduction process of In(III) ions in chlorates(VII). These substances are adsorbed on mercury from chlorates(VII). The relative surface excesses of thiourea and its derivatives increase with the increase of their concentrations and electrode charge. After adding thiourea, N-methylthiourea, N,N′-dimethylthiourea and N-allylthiourea to the solution an acceleration of the electroreduction process of In(III) ions occurs. This process depends on two factors: the adsorption of an accelerating substance on mercury and on the formation of complexes between a depolarizer and an accelerating substance on the electrode surface. The equilibrium of this complexing reaction determines the magnitude of the catalytic effect.     

“Cap-Pair” Effect as the Reason of the Catalytic Properties of Nicotinic Acid: Experimental and Theoretical Studies

The influence of nicotinic acid (NC) on the kinetics and the mechanism of electroreduction of Zn²⁺ ions in the acetate buffer (pH=6.0) was investigated using electrochemical methods (EIS, CV, SWV and DC). It was shown that the anions of NC catalyze the electrode reaction (cap-pair effect) by adsorbing on the surface of the mercury electrode. The catalytic activity of NC is due to its ability to form active NC−Zn²⁺ complexes on the electrode surface, facilitating the electron transfer process. However, no evidence of the formation of such complexes in the solution was found using classical molecular dynamics. Moreover, it was proved that the electroreduction of Zn²⁺ ions in the presence of NC is a two-stage process. The first stage involves the transfer of the first electron, preceded by the partial loss of the hydration shell by the Zn²⁺ ions and formation of the active complex. Moreover, it was shown that in the range of lower concentrations, c≤1.10⁻² mol.dm⁻³, the nicotinic acid shows weaker catalytic abilities than another form of vitamin B3 – nicotinamide. In the range of its higher concentrations, the nicotinic acid is a more effective catalyst for the electroreduction of Zn²⁺ ions.     

On the mechanism of electroreduction of sulphur-containing ligands induced by the electroreduction of transition metal cations

The large scale electrolysis of Zn(II), Cd(II), Hg(II), Cu(II), Ni(II), Co(II), Co(III), Fe(II), Mn(II), Cr(II), Cr(III), Bi(III), In(III) and Sb(III) at mercury electrodes in presence of mercaptoacetic acid, 3-mercaptopropionic acid, cysteine and thiourea was carried out and the products were investigated. In case of transition metal ions the catalytic reduction of organic compounds resulting in the formation of sulphide ions was found. There are two possible ways of the production of these ions: (i) consisting in the formation of a complex between transition metal ion and organic ligand which is subsequently, reduced, and (ii) direct electroreduction of organic compound on the electrode modifiied by the deposition of metal and metal sulphide. For both cases the mechanism of electroreduction was discussed.     

Accelerating Effect of Tetramethylthiourea on the Kinetics of Zn2+ Electroreduction

The results of kinetic measurements of Zn²⁺ electroreduction on mercury electrode in the presence of tetramethylthiourea showed the two‐step character of the electrode process. The acquisition of nonlinear wide potential range Tafel plots was found to offer a good opportunity to examine the Zn²⁺ electroreduction mechanism. Three mechanisms including the ion transfer step followed by the electron exchange step (IE mechanism), the adsorption step (IA mechanism) and the chemical step followed by electron transfer (CE) were applied. The accelerating influence of tetramethylthiourea on Zn²⁺ electroreduction was found to result from possible complexes formation in the diffuse layer. The ion transport step is probably combined with the loss or exchange of a ligand. The second step probably consists in the electron transfer or adsorption process connected with partial charge transfer.     

Studies of the mixed adsorption layer on a mercury electrode in the systemp-toluidine-polyethyleneglycol-1M NaClO4

Summary The properties of the mixed adsorption layer on a mercury electrode in the system 1M NaClO₄-p-toluidine-polyethyleneglycol (average molecular masses of polyethyleneglycols: 400 or 10000) are discussed. The parameters of theFrumkin and virial isotherms were determined in the range of strong adsorption potentials. In the range of more negative potentials, a mixed adsorption layer was found by investigating the kinetics of the reduction of Zn(II) ion as a pilot ion. Depending on the concentration ratio of the studied organic substances, inhibition, acceleration, or compensation of both with respect to Zn(II) electroreduction was observed. In the presence of polyethyleneglycol, the efficiency of the Zn(II) ion electroreduction increases due to a greater adsorption lability ofp-toluidine molecules on the mercury surface.

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Untersuchung der gemischten Adsorptionsschicht an einer Quecksilberelektrode im Systemp-Toluidin-Polyethyleneglycol-1M NaClO₄

Zusammenfassung Die Eigenschaften der gemischten Adsorptionsschicht an einer Quecksilberelektrode trode im System 1M NaClO₄-p-Toluidin-Polyethyleneglycol(durchschnittliche Molmassen der Polyethylenglycole: 400 bzw. 1000) werden diskutiert. Die Parameter derFrumkin- und Virialisotherme wurden im Bereich hoher Adsorptionspotentiale bestimmt. Im Bereich negativerer Potentiale wurde durch Untersuchung der Kinetik der Elektroreduktion von Zn(II)-Ionen als Pilotionen eine gemischte Adsorptionsschicht gefunden. In Abhängigkeit von der Konzentration der organischen Verbindungen beobachtet man bezüglich der Elektroreduktion von Zn(II) Hemmung, Beschleunigung oder eine gegenseitige Kompensation beider Effekte. In Gegenwart von Polyethyleneglycol nimmt die Effizienz der Elektroreduktion von Zn(II) aufgrund einer höheren Adsorptionslabilität derp-Toluidin-Moleküle an der Quecksilberoberfläche zu.

     

Keggin型缺位磷钨杂多阴离子的电化学性质及电催化还原过氧化氢

循环伏安实验显示, 缺位磷钨杂多阴离子 的酸性水溶液在玻碳(GC)电极上有两对可逆的还原-氧化波. 第一对波的电荷迁移数为1.4, 有2个质子参与反应; 第二对波的电荷迁移数为1.0, 参加电极反应的质子数为1. 根据峰电流与电位扫描速率平方根的关系得到 在0.1 mol•L－1 NaOAc＋HOAc溶液中的扩散系数 Do为3.54×10－6 cm2•s－1. 交流伏安和交流阻抗实验表明, 的电极过程包含吸附和脱附步骤, 第一对波的电荷迁移阻抗较大, 第二对波的较小, 对应的交换电流密度i0分别为4.6×10－5和6.7×10－4 A•cm－2. 电极过程的可逆性及其缺位特性使它对H2O2的还原有显著的电催化作用, 因此有望用于有机物的氧化和降解. 同时, 还提出了一个相关的电催化机理.     

Investigations into the electroreduction of copper(II) ions on chalcocite in ammonia solutions using the rotating disc electrode method

Investigations into the electroreduction of copper(II) ions in ammonia solutions on a disc electrode made of synthetic chalcocite having a deficiency of copper atoms have been presented. It has been concluded that within the range of the diffusion controlled process copper(II) ions are the diffusing substance, at the same time in the course of the reaction two electrons are exchanged. The kinetic parameters for the electroactivating process have been estimated. With a higher concentration of copper in solution an inhibition process has been observed, probably caused by a slow transport rate of the species in the material of the electrode. In the system studied the phenomenon of a partially blocked electrode surface does not occur according to the Landsberg model.     

Intermolecular Interactions in Systems Containing Bi(III) – ClO−4 – H2O – Selected Amino Acids in the Aspect of Catalysis of Bi(III) Electroreduction

The paper describes recent results of studies on the accelerating effect of sulfur‐containing protein amino acids and water activity on multistep Bi(III) ion electroreduction at mercury electrode. The catalytic effect of methionine (Mt), cystine (CY) and cysteine (CE) was analyzed based on kinetic and thermodynamic parameters, which correlated with water activity. Investigations of adsorption of those amino acids at the electrode/solution interface provided information for the analysis of the electrical double layer and its influence on the kinetics of the electrode process. The multistep Bi(III) electroreduction process is controlled by the kinetics of active complexes formation, which precedes transfer of consecutive electrons.     

Electroenzymatic reactions with oxygen on laccase-modified electrodes in anhydrous (pure) organic solvent

The electroenzymatic reactions of Trametes hirsuta laccase in the pure organic solvent dimethyl sulfoxide (DMSO) have been investigated within the framework for potential use as a catalytic reaction scheme for oxygen reduction. The bioelectrochemical characteristics of laccase were investigated in two different ways: (i) by studying the electroreduction of oxygen in anhydrous DMSO via a direct electron transfer mechanism without proton donors and (ii) by doing the same experiments in the presence of laccase substrates, which display in pure organic solvents both the properties of electron donors as well as the properties of weak acids. The results obtained with laccase in anhydrous DMSO were compared with those obtained previously in aqueous buffer. It was shown that in the absence of proton donors under oxygenated conditions, formation of superoxide anion radicals is prevented at bare glassy carbon and graphite electrodes with adsorbed laccase. The influence of the time for drying the laccase solution at the electrode surface on the electroreduction of oxygen was studied. Investigating the electroenzymatic oxidation reaction of catechol and hydroquinone in DMSO reveals the formation of various intermediates of the substrates with different electrochemical activity under oxygenated conditions. The influence of the content of aqueous buffer in the organic solvent on the electrochemical behaviour of hydroquinone/1,4-benzoquinone couple was also studied.     

Polarographic studies of chemical reactions preceding electron transfer (review)

The review is dedicated to theory and experimental applications of polarography for studies of consecutive and parallel chemical reactions preceding electron transfer and occurring in the bulk or surface (adsorption) reaction layers. The methodology of finding kinetic and equilibrium parameters including formal potentials is presented. The following chemical reactions are considered: (1) protonation of anions of benzene polycarboxylic acids; (2) dehydration (decyclization) and protonation of carbonyl compounds; (3) proton exchange between mixed solvent molecules; (4) formaldehyde-amine interaction; (5) complexation with the ligand catalyzing electroreduction of metal ions; (6) dissociation of metal complexes; (7) formation of deposits of metal hydroxides with parallel oxygen reduction.     

Oxygen reduction reaction on polycrystalline gold. Pathways of hydrogen peroxide transformation in the acidic medium

The mechanism of oxygen electroreduction on polycrystalline gold is studied in the acidic medium. Hydrogen peroxide is the main reaction product. However, two potential regions can be singled out in which the oxygen electroreduction reaction proceeds by different pathways. The first region is the potential interval close to the steady-state potential. Here, the oxygen electroreduction virtually completely produces peroxide. The second interval is the potential range of considerable cathodic polarization values. In this case, peroxide can be reduced to water. The low energy of hydrogen peroxide adsorption on gold determines the considerable overpotential of peroxide reduction. It is shown that on the gold electrode surface, the catalytic decomposition of peroxide occurs. The use of the method of electrochemical impedance spectroscopy allows the peculiarities of the oxygen reaction associated with hydrogen peroxide transformations to be revealed. In the acidic medium, the reactions of consecutive reduction of oxygen through the intermediate formation of hydrogen peroxide and the catalytic decomposition of the intermediate product are shown to proceed simultaneously. The ratio of rate constants of electrochemical stages depends on the potential. The chemical decomposition is observed both near the steady-state potential and in the cathodic region where considerable electrochemical reduction of peroxide occurs.     

Hydrogen Evolution on a Mercury Electrode: The Effect of a Condensed Adsorption Layer

The electroreduction of hydrogen on a dropping mercury electrode with and without condensed adsorption layers (CAL) of organic compounds is studied by methods of classical polarography and laser photoemission. An analysis of effects CAL has on some reactions reveals that the CAL influence on the first-electron transfer and on reactions involving intermediates can retard or even completely block the process. The most profound changes occur in the processes that involve a proton donor. Possible reasons for different effects of CAL on the electron transfer processes are discussed.     

The mechanism of tin-promoted electrochemical oxidation of organic substances on platinum

The promoting action of tin in the binary system platinum tin has been studied. A direct correlation of polarization and adsorption measurements has been carried out using an adsorption method of applying the promoter. The method of fast potentiodynamic pulses has been used to control the amount of tin and organic species on the surface. Studies have been made with smooth and platinized electrodes on the adsorption and oxidation of formic acid and methanol. A comparison of electro-oxidation rates at constant organic species coverage has made it possible to reveal the true catalytic effect as a result of introduction of tin. This effect has been found to be independent of both the nature of the substance under oxidation and the state of the electrode surface (smooth or rough). The promoting effect of tin is observed in the reactions where the limiting stage is represented by R+OH_ads; in the reactions where the limiting stage is represented by electron transfer or else the interaction R+H_ads, the promoting effect of tin does not show up, which fact points to the selectivity of its catalytic action.     

The electrochemistry of chromium in molten LiCl+KCl

Chronopotentiometric and steady-state voltammetric techniques have been employed to study the electroreduction processes:Cr(III)+eCr(II) andCr(II)+2eCr(0) separately, using the LiCl+KCl eutectic as solvent at 500°C.The adsorption of the ions on the electrode surfaces appears to play a role in the overall electrode processes; the degree of adsorption was correlated with the variation of exchange current density with concentration in the case of the Cr(II) ions. Fluoride ions had no effect on the electrode processes. The chronopotentiometric behaviour of Cr(III) ions was rather complex but adsorption appeared to play a part in this case also.     

Electroreduction of some pyridine carboxamides on carbon electrodes in aqueous solutions

The electroreductions of the NAD⁺ model compounds nicotinamide (I), N₁-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H⁺ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes.     

Study of the Complexation,Adsorption and Electrode Reaction Mechanisms of Chromium(VI) and (III) with DTPA Under Adsorptive Stripping Voltammetric Conditions

The complexation of Cr(III) and Cr(VI) with diethylenetriaminepentaacetic acid (DTPA), the redox behavior of these complexes and their adsorption on the mercury electrode surface were investigated by a combination of electrochemical techniques and UV/vis spectroscopy. A homogenous two‐step reaction was observed when mixing Cr(III), present as hexaquo complex, with DTPA. The first reaction product, the electroactive 1 : 1 complex, turns into an electroinactive form in the second step. The results indicate that the second reaction product is presumably a 1 : 2 Cr(III)/DTPA complex. The electroreduction of the DTPA‐Cr(III) complex to Cr(II) was found to be diffusion rather than adsorption controlled.The Cr(III) ion, generated in‐situ from Cr(VI) at the mercury electrode at about ?50 mV (vs. Ag|AgCl) (3 mol L^?1 KCl), was found to form instantly an electroactive and adsorbable complex with DTPA. By means of electrocapillary measurements its surface activity was shown to be 30 times higher than that of the complex built by homogenous reaction of DTPA with the hydrated Cr(III). Both components, DTPA and the in‐situ built complex Cr(III) ion were found to adsorb on the mercury electrode.The effect of nitrate, used as catalytic oxidant in the voltammetric determination method, on the complexation reaction and on the adsorption processes was found to be negligible.The proposed complex structures and an overall reaction scheme are shown.     

Electroreduction of oxygen on copper-containing sulfide minerals

The state of the surface of and the oxygen electroreduction on the naturally occurring minerals bornite, chalcopyrite, and chalcosine are studied in borate buffer solutions using X-ray photoelectron spectroscopy, cyclic voltammetry, and the rotating disk electrode technique. The surface of the minerals in an oxygen-containing atmosphere is covered with compounds of copper and iron in the highest oxidation states, and the oxygen electroreduction occurs on these compounds. Electrocatalytic activity of sulfide minerals during cathodic polarization is presumably due to the participation in the oxygen electroreduction reaction of redox centers, i.e. ions of Fe(II) in bornite and chalcopyrite, and ions of Cu(I) bonded with the sulfide sulfur in each of the minerals.     

The mechanism of electroreduction of nitrate ions on a hybrid electrode nanodispersed copper-MK-40 membrane

Based on a MK-40 sulfocation-exchange membrane, a hybride electrode material containing nanodispersed copper is prepared. The methods of scanning electron microscopy and X-ray diffraction (XRD) analysis reveal the formation of copper agglomerates measuring 250–470 nm and consisting of individual particles of 20–30 nm. The procedure of multistage chemical deposition of copper into the ion-exchange carrier makes it possible to obtain a continuous cluster of metal particles which determines the electron conducting properties of the resulting hybrid material. The electrochemical activity of the nanocomposite electrode is studied in the reaction of nitrate ion electroreduction. Nanodispersed copper deposited into the membrane is shown to intensify the electroreduction of nitrate ions by a factor of 1.5–2 as compared with a compact copper electrode. The electroreduction of nitrate ions on compact copper is shown to involve 6 electrons, whereas the electroreduction on the nanocomposite involves 8 electrons. The electroreduction products of nitrate ions are identified by the IR spectroscopy method.     

Mechanism of adsorption,electroreduction and hydrogenation of compounds with ethylenic bonds on platinum and rhodium: Part II. Comparison of the electroreduction and catalytic hydrogenation processes

The catalytic liquid-phase hydrogenation of maleic acid on platinum and rhodium has been investigated. It is shown that the rate-determining step of this process as well as of the electroreduction process of maleic acid is the interaction of the chemisorbed particle of maleic acid with the adsorbed hydrogen which is formed at the preceding rapid stage of either the dissociative adsorption of molecular hydrogen, or the electrochemical stage of hydrogen ion discharge. The rate of the process with the same degree of surface coverage with hydrogen and chemisorbed particles of maleic acid does not depend on whether the process is carried out catalytically or electrochemically, on whether maleic acid and hydrogen were preliminarily adsorbed on the surface of the electrode-catalyst or not. With due regard for the mutual influence of chemisorbed particles participating in the rate-determining stage, the main kinetic equations for the electroreduction and catalytic hydrogenation processes have been derived. The difference in the rates of electroreduction of maleic acid on platinum and rhodium, with the same degree of electrode surface coverage with reactants, is shown to be the result of differences in the adsorption heats (or bonding strength with the surface) of hydrogen and maleic acid on these two metals. Experimental procedures are described in Part I [1].