New Electrocatalytic Reactions at a Mercury Electrode in the Presence of Homocysteine or Cysteine and Cobalt or Nickel Ions

Homocysteine (Hcy) and cysteine (Cys) mercury thiolate layers were prepared by anodic polarization of a mercury electrode in amino acid containing solutions and then investigated in the cathodic regime in the presence of Ni²⁺ or Co²⁺ ions. The sulfhydryl function in the mercury thiolate undergoes a slow disintegration resulting in surface‐attached mercury sulfide. During the cathodic scan, Hg²⁺ substitution by Ni²⁺ or Co²⁺ yields minute amounts of the relevant metal sulfide. Such a species catalyzes hydrogen evolution at ?1.3 V vs. Ag|AgCl|KCl(3 M). Hcy experiences a faster decomposition and, consequently, displays a stronger catalytic effect. Each compound catalyzes the reduction of Ni²⁺ or Co²⁺, but only Cys (bound in metal complexes) induces typical catalytic hydrogen evolution processes such as the Brdi?ka reaction (with Co²⁺; pH around 9), or the catalytic hydrogen prewave (CHP) (with Ni²⁺; pH near 7). On the other hand, Hcy catalyzes the hydrogen evolution in the presence of Co²⁺ at ?1.5 V in the same way than sulfur derivatives with no amine function do. Metal sulfide formation does not interfere with CHP and Brdi?ka processes. Correlations between the physical state of the metal sulfide (adsorbed molecule or aggregate form) and its catalytic properties are discussed and possible analytical applications suggested.     

The effect of chemisorbed sulfide ions on the gold electrodeposition from acidic thiocarbamide electrolytes

Introducing sodium sulfide (about 10^?5 M) into acidic thiocarbamide solutions reduces the gold reduction overpotential. The reaction rate passes through a maximum at a potential of 0.1 V. The overpotential depends on the sulfide ion concentration and the time of electrode exposure to solution prior to the beginning of scanning. Transients of potential measured on a renewable gold electrode in thiocarbamide electrolytes containing catalytically active species served as the basis for calculations of the coefficient of trapping of sulfide ions by the growing gold deposit. The kinetics of gold electrodeposition at fixed surface coverages with adsorbed sulfide ions θ is studied. It is shown that at θ = const, the dependence of the reaction rate on the overpotential is described by the Tafel equation. It is shown that with an increase in θ, the effective values of exchange current and transfer coefficient increase from i ₀ ≌ 10^?5 A/cm² and α ≌ 0.25 in pure solutions to α ≌ 0.5 and i ₀ ≌ 10^?4 A/cm² at θ ≥ 0.3 and then remains virtually unchanged. The reaction order decreases in the absolute magnitude, remaining negative. Thus for θ ≌ 0, p _k = ?logi/?logc = ?1, whereas for θ ≥ 0.3, p _k = ?0.3. A possible explanation is proposed for the catalytic effect of the sulfide ion adsorption on the mechanism of the gold reduction from acidic thiocarbamide electrolytes.     

A Four‐Electron Sulfur Electrode Hosting a Cu2+/Cu+ Redox Charge Carrier

The elemental sulfur electrode with Cu²⁺ as the charge carrier gives a four‐electron sulfur electrode reaction through the sequential conversion of S?CuS?Cu₂S. The Cu‐S redox‐ion electrode delivers a high specific capacity of 3044 mAh g^?1 based on the sulfur mass or 609 mAh g^?1 based on the mass of Cu₂S, the completely discharged product, and displays an unprecedently high potential of sulfur/metal sulfide reduction at 0.5 V vs. SHE. The Cu‐S electrode also exhibits an extremely low extent of polarization of 0.05 V and an outstanding cycle number of 1200 cycles retaining 72 % of the initial capacity at 12.5 A g^?1. The remarkable utility of this Cu‐S cathode is further demonstrated in a hybrid cell that employs an Zn metal anode and an anion‐exchange membrane as the separator, which yields an average cell discharge voltage of 1.15 V, the half‐cell specific energy of 547 Wh kg^?1 based on the mass of the Cu₂S/carbon composite cathode, and stable cycling over 110 cycles.     

Normal pulse polarographic quantification of cyanide and sulfide by the anodization of mercury

Normal pulse polarography is used to quantify cyanide and sulfide simultaneously by the anodic oxidation of mercury. The detection limit for cyanide is 18 μg l^-1 by the normal pulse polarographic technique. A supporting electrolyte system of 1 M Na₂CO₃ is optimal with regard to background interferences and sample loss. The electrode reaction for the oxidation of mercury in the presence of cyanide can be described by Hg + pCN^- α Hg(CN)_p^2-p + 2e^-, with p having values of 2, 3 and 4 depending on the surface concentration of cyanide. The feasibility of simultaneous cyanide and sulfide quantification is demonstrated with waste-water samples.     

The effect of potential on the gold dissolution in cyanide solutions in the presence of sulfide ions

The effect of potential on the rate of gold dissolution in the cyanide solutions in the presence of sulfide ions is studied. The dependences of current on the time after the electrode surface renewal were measured under the potentiostatic conditions. The majority of experiments were performed in the solution of the following composition, M: 0.1 KCN, 0.1 KOH, 0.01 KAu(CN)₂, (1.5–2) × 10^?5 Na₂S at 23°C. It is shown that, at the potentials more positive than ?0.1 V (NHE), the rate of gold dissolution starts to increase as soon as the surface is renewed, which is associated with high-rate chemisorption of catalytically active sulfide ions. At E < ?0.1 V, the chemisorption proceeds slowly, and a considerable increase in the current takes much time. Therefore, in the potentiodynamic measurements, at E < ?0.1 V, no catalytic effect of sulfide ions is observed. When the ratio between the concentrations of sulfide and cyanide ions is decreased, the potential, which, by convention, bounds the aforementioned ranges, shifts in the positive direction. Plausible explanations for these regularities are proposed.     

Characterization of Iron Sulfide Species in Model Solutions by Cyclic Voltammetry. Revisiting an Old Problem

A long‐standing problem associated with voltammetric determination of iron and sulfide in reduced natural waters has been the nature of the presumed analyte responsible for a reduction peak at ?1.1 V vs. Ag/AgCl. Cyclic voltammetry at the Hg electrode is used here to study solutions with different Fe(II) to sulfide ratios in chloride and acetate electrolytes (pH 6–7). The results indicate that the ?1.1 V peak can be assigned to reduction of Fe²⁺ or its labile complexes on FeS layers that partially cover the Hg electrode. Hg electrodes covered with FeS act like FeS solid electrodes over a very wide potential range (?0.35 to ?1.9 V). Two mechanisms for forming FeS layers on Hg are described. Over the broadest deposition potential range, the dominant mechanism involves attachment at the Hg surface of FeS nanoparticles, which are generated quickly in initially supersaturated mixtures of Fe(II) and S(–II). In a narrow deposition potential range, roughly ?0.56 to ?0.70, FeS layers are produced additionally by replacement of preformed HgS. Because Fe²⁺ is reduced at ?1.1 V on FeS layers and at ?1.4 V on bare Hg, it may be underdetermined when only the ?1.4 V peak is measured.     

Quartz crystal microbalance measurements of kinetic parameters of anodic dissolution of gold in thiocarbamide electrolytes in the presence of sulfide ions

As shown by quartz-crystal microbalance measurements, in the potential range from 0.0 to 0.55 V (NHE), sulfide ions adsorbed on the gold electrode surface accelerate the electrode reaction of anodic dissolution of gold in acidic thiocarbamide solutions. The microbalance determination of kinetic parameters at a constant electrode surface coverage with sulfide ions includes a special procedure developed for the determination of the gold dissolution rate. The conditions (the potential range and the potential scan rate) of independence of the dissolution rate from the diffusion limitations associated with the ligand delivery is determined. Under these conditions, the polarization curve is shown to be linear on semilogarithmic coordinates and correspond to the Tafel equation. In this potential range, the transfer coefficient α and the reaction order with respect to the ligand p are determined at a constant electrode surface coverage θ with adsorbed sulfide ions. It is shown that with the transition from the surface coverage with sulfide ions θ = 0.1 to θ = 0.8, the transfer coefficient α changes from 0.25 to 0.55, the exchange current (i ₀) changes from 10^?5 to 5 × 10^?5 A/cm², and the effective reaction order p with respect to the ligand changes from 0.2 to 1.3. The mentioned changes are associated not only with the acceleration of gold dissolution in the presence of chemisorbed sulfide ions but also with the changeover in the mechanism of this process. Quartz-crystal microbalance data on the gold dissolution rate qualitatively agree with the results of voltammetric measurements of a renewable gold electrode. A possible version of explanation of the catalytic effect of sulfide ion adsorption on the gold dissolution is put forward.     

Fundamental problems of water splitting at cadmium sulfide

Oxygen is directly involved in the anodic photocorrosion of CdS leading to sulfate formation according to the overall reaction CdS + 4h⁺ + 2H₂O + O₂ → Cd²⁺ + SO²⁻₄ + 4H⁺. Sulfate formation leads to cleaning of the CdS surface from elemental sulfur and therefore improves the electrode behaviour dramatically. Removal of sulfur from the surface shifts the flatband potential of CdS to about −1.7 V(SCE) and the valence-band edge to −0.6 V(SCE). Accordingly holes lose their thermodynamic capability to oxidise water.     

Kinetics of silver electrodeposition from thiocarbamide solutions at a regular surface coverage with sulfide ions

Kinetics of silver electrodeposition in the presence of sulfide ions is studied on electrodes renewed by cutting off a thin surface layer, at a controlled time of contact of the “fresh” surface with the electrolyte. Solutions containing 10^?2 M AgNO₃, 0.1 M thiocarbamide, 0.5 M HClO₄, and from 2 × 10^?6 to 1.5 × 10^?5 M Na₂S are studied. It is shown that under the studied conditions, the effect of silver electrodeposition on the surface concentration of sulfide ions is insignificant. As the concentration of sulfide ions in solution and their coverage on the electrode surface θ increase, the cathodic polarization decreases. Tafel curves plotted for θ = const are used in estimating the exchange current i ₀ and the transfer coefficient α. It is shown that α ≈ 0.5 and weakly depends on θ, whereas the exchange current increases with the increase in θ by an approximately linear law from 10^?5 A/cm² at θ ? 0 to 10^?4 A/cm² at θ = 0.43. The obtained data are compared with the results of kinetic studies of silver anodic dissolution in similar solutions.     

Electrochemical nanogravimetric studies of sulfur/sulfide redox processes on gold surface

Electrochemical quartz crystal microbalance, combined with cyclic voltammetric, chronoamperometric, and potentiostatic measurements, was used to study electrodeposition/dissolution phenomena at a gold electrode in solutions containing Na₂S. Spontaneous, open-circuit deposition processes as well as dissolution of the deposits in sulfide-free solutions have also been investigated. The potential range, scan rate, sulfide concentration, and pH have been varied. The results of the piezoelectric nanogravimetric studies are elucidated by a rather complex scheme involving underpotential deposition of sulfur at approximately −0.85 V vs. sodium calomel electrode, reductive dissolution of the deposited sulfur-containing layer at potentials more negative than approximately −0.9 V, and formation of a sulfur-containing multilayer at potentials more positive than −0.2 V. During the reduction of sulfur deposited on Au, a mass increase due to the formation of polysulfide species in the surface layer, accompanied by incorporation of Na⁺ counterions, can be observed that starts at approximately −0.4 V. This is a reversible process, i.e., during the reoxidation, counterions leave the surface layers. Frequency excursions during the electroreduction and reoxidation processes reveal existence of several competitive dissolution–deposition steps. Spontaneous interaction between Au and HS⁻ species results in a surface mass increase at the open-circuit potential, and it also manifests itself in the substantial decrease of the open-circuit potential after addition of Na₂S to the supporting electrolyte.     

Influence of sulfide and cyanide ions on the electrochemical behavior of the Fe(II)/Fe(Hg) system in thiocyanate solutions at mercury electrodes

The reduction and reoxidation processes of the Fe(II)/Fe(Hg) system in thiocyanate solutions at stationary mercury electrodes have been investigated by cyclic voltammetric, anodic stripping and controlled potential electrolysis methods. In 0.1 M NaSCN and 0.4 M NaClO₄ solution containing 1×10^?3M Fe(II), the voltammogram on the first cycle at. 0.05 V s^?1 gives two consecutive cathodic peaks near ?1.2 and ?1.39 V with a hysteresis on the reversal, and an anodic wave with two large peaks near ?0.58 and ?0.05 V and two small peaks near ?0.52 and ?0.43 V, respectively. The multicyclic voltammogram under the same conditions in the potential region between 0.00 and ?1.50 V gives a cathodic wave with a principal peak near ?1.02 V and two small peaks near ?0.02 and ?0.53 V, respectively, and an anodic wave with a principal peak near ?0.72 V, three small peaks near ?0.64, ?0.52 and ?0.40 V, and with a shoulder near ?0.05 V, respectively. The variation of the shape of the voltammogram on the second and subsequent runs is due to the formation of S^2? and CN^? during the process of electroreduction of Fe(II). A mechanism is proposed which involves an initial reduction of Fe(II)?SCN^? produced in an activation step at a mercury electrode, followed by the chemical redox reaction of a part of Fe(0)?SCN^? in the species giving FeS and CN^?, and takes into account the influence of FeS and CN^? on the further reduction and reoxidation of iron. Both FeS and CN^? stimulate further reduction, and reoxidation of iron. The hysteresis of the cathodic wave on the first cycle arises from the fact that Fe(II) is reduced more easily at the mercury electrode covered with FeS than at a pure mercury electrode.     

The molecular mechanism of low-temperature decomposition of hydrogen sulfide under conjugated chemisorption-catalysis conditions

The molecular mechanism of interaction of two hydrogen sulfide molecules with the (Co^III-H_o)₂S₂(SH₂)₄ model active center containing occluded hydrogen was studied by the density functional theory method with the B3P86 hybrid exchange-correlation functional. The reaction was found to occur in the following elementary steps: molecular adsorption of hydrogen sulfide ? dissociative chemisorption ? S-S bond formation in the surface intermediate {2Co^III ? (μ-S₂) + 2H(ads)} with the release of the first hydrogen molecule into the gas phase H₂(g) ? the release of the second hydrogen molecule into the gas phase H₂(g) ? the formation of cyclooctasulfur in the reaction 4S₂(ads) → S₈(ads). The first three steps occur spontaneously at room temperature, the thermodynamic driving force of the process being the stoichiometric reaction of S-S bond formation at the stage of conjugated chemisorption of two hydrogen sulfide molecules on two adjacent metal ions with the release of the first hydrogen molecule into the gas phase. The catalytic cycle is terminated by the recombination of molecular sulfur S₂ into cyclooctasulfur S₈ in the adsorption layer and the release of the second hydrogen molecule into the gas phase.     

Contribution from the ion-exchange factor to the potential of a copper-containing electron-ion exchanger

The process of formation of the electrode potential of EI-21 electron-ion exchanger, composed of ultrafine copper particles and KU-23 sulfocationite, was studied. The potentials of a EI-21 powdery electrode with a platinum lead in copper(II) sulfate solutions of various concentrations (0.005–1.0 M) were measured using currentless-mode potentiometry. The potential of this electrode first shifted by 0.02–0.15 V in the negative direction with respect to a compact copper electrode, after which the shift eventually decreased to ?0.010 ± 0.003 V. It was demonstrated that the time evolution of the potential is determined by the interplay of electron and ion exchange. When EI-21 is placed onto a platinum lead, the role of the potential-determining reaction passes from Cu²⁺ + e^? ? Cu⁺ to Cu²⁺ + 2e^? ? Cu. At the same time, H⁺-Cu²⁺ ion exchange gives rise to a change in the ratio of the concentration of copper(II) ions in the internal and external solutions. The Donnan potential, which arises at the boundary between the electron-ion exchanger and the external solution, maintains a high concentration of copper(II) ions in the internal solution, a factor that facilitates the recrystallization of the particle distributed over the bulk of the exchanger. The process of recrystallization slows down with time to such an extent that the electrode potential stops changing, remaining at a level close to the equilibrium potential of the Cu²⁺/Cu pair. It was concluded that the internal stability of the system makes the potential of the EI-21 electrode sensitive to the dispersity of the metal component and the concentration of potential-determining metal ions in the external solution.     

Investigation of the interaction between Co sulfide coatings and Cu(I) ions by cyclic voltammetry and XPS

The interaction between the Co sulfide coating formed on a glassy carbon electrode and Cu(I)-ammonia complexes solution was investigated by cyclic voltammetry in 0.1 M KClO₄, 0.1 M NaOH and 0.05 M H₂SO₄ solutions. It was determined that, after treating the cobalt sulfide coating formed by two deposition cycles with Cu(I)-ammonia complexes (0.4 M, pH 8.8–9.0, τ=180 s, T=25±1°C), an exchange occurs between the coating components and Cu(I). Copper(I) substitutes 75% of the Co(III) compounds present in the coating (~1.81×10^–7 mol cm^–2) because of Cu₂O (1.36×10^–7 mol cm^–2) formation. The rest of the Co(II) and Co(III) sulfide compounds are also replaced by copper with formation of Cu_{2– x} S with a stoichiometric coefficient close to 2 (~1.9). After modifying the cobalt sulfide coatings with Cu(I) ions, the total amount of metal (Co+Cu) increases, owing to the sorption of Cu(I) compounds. In addition, the number of deposition cycles decreases from 3 to 1.5 [1 cycle involves cobalt sulfide layer formation and 0.5 cycle is attributed to modifying by Cu(I) ions]. The coatings modified in the above-mentioned manner may be successfully used for plastic electrochemical metallization as Cu_{2– x} S coatings formed by three deposition cycles. Electronic Publication     

Electrochemical properties of lanthanum nickel oxide

Electrochemical properties of lanthanum nickel oxide, LaNiO₂₈₄, were studied in alkaline solutions. It was concluded that redox reactions of Ni⁴⁺/Ni³⁺ and Ni³⁺/Ni²⁺ in a solid surface layer took place at 0.4 V and ?0.4 V (vs. Hg/HgO), respectively. As the conductivity of the oxide is a function of the oxygen concentration due to σ^* bond formation, the resistivity of the electrode was changed depending on polarization potentials. The catalytic activity for oxygen reduction of a preoxidized electrode seemed to be higher than that of an electrode not intentionally oxidized, and the activity depended on the concentration of the alkaline solution. It was presumed that Ni³⁺ cations which form the σ^* bond with oxygen have an important role in the electrocatalysis of oxygen reduction on lanthanum nickel oxide.     

Electrochemical Evaluation of Pollutants in the Environment: Interaction Between the Metal Ions Zn(II) and Cu(II) with the Fungicide Thiram in Billings Dam

Pesticides are organic molecules used in the control of various pests in different crops. These molecules show functional groups that can interact with metal ions, forming new species with different properties. These new compounds have been attracting attention because they can become a new environmental problem. In this work the interaction of copper and zinc metal ions with Thiram pesticide was studied using electrochemical techniques. Studies in ultrapure water showed the formation of Zn?Thiram complex with reduction potential at ?1.330 V; Cu?Thiram complex showed a cathodic peak at 0.020 V. Thiram causes a different effect on the two metal ions studied. It was observed that the ligand stabilizes more the Cu(II) than Zn(II). Both systems proved to be quasi‐reversible, controlled by the adsorption of the species on the electrode surface. The formation constants of the complexes were calculated to be 2.1×10⁵ for Zn?Thiram and 1.5×10¹⁹ for Cu?Thiram. In the samples from Billings dam, the Zn‐complex showed reduction potential at ?1.403 V; Cu‐complex exhibited a reduction peak at 0.012 V. Although there are interferers in river waters, the interaction of these metals with the pesticide showed high affinity, being possible to detect them in natural samples. The Cu(II) complex showed to be more stable in natural matrices when compared to the Zn(II) complex. The sensitivity for thiram electroanalytical determination decreases in the presence of Zn(II) and Cu(II).     

Amperometric determination of sulfide ion by glassy carbon electrode modified with multiwall carbon nanotubes and copper (II) phenanthroline complex

Electrocatalytic oxidation of sulfide ion on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNTs) and a copper (II) complex was investigated. The Cu(II) complex was used due to the reversibility of the Cu(II)/Cu(III) redox couple. The MWCNTs are evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on Cu(II) complex adsorbed on MWCNTs immobilized on the surface of GCE. The modified GCE was applied to the selective amperometric detection of sulfide at a potential of 0.47 V (vs. Ag/AgCl) at pH 8.0. The calibration graph was linear in the concentration range of 5 µM–400 µM; while the limit of detection was 1.2 µM, the sensitivity was 34 nA µM^?1. The interference effects of SO₃ ^2?, SO₄ ^2?, S₂O₃ ^2?, S₄O₆ ^2?, Cysteine, and Cystein were negligible at the concentration ratios more than 40 times. The modified electrode is more stable with time and more easily restorable than unmodified electrode surface. Also, modified electrode permits detection of sulfide ion by its oxidation at lower anodic potentials.      

Effect of hydrogen sulfide on the iron dissolution rate in a sodium sulfate solution under natural aeration conditions

The influence of hydrogen sulfide (10–100 mg/1) on the Armco iron anodic dissolution in an aerated 0.17 M Na₂SO₄ solution is investigated. During a potentiostatic anodic polarization, the hydrogen sulfide introduction makes the current increase stepwise. The magnitude of the increase depends on the duration of preliminary anodic polarization, electrode potential, and hydrogen sulfide concentration. The anodic metal dissolution activation by hydrogen sulfide is explained by chemical conversion of the oxide-hydroxide passivating film into iron sulfide that is generated at the metal surface in the form of a porous film and does not hinder the electrode dissolution. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Gold Dissolution Electrocatalysis in Thiourea Electrolytes in the Presence of Chemisorbed Sulfide Ions

Adding a microscopic quantity of sodium sulfide (～10^?5 M) into acid solutions of thiourea leads to a dramatic acceleration of anodic dissolution of gold. The acceleration effect is greater at larger thiourea concentrations (c) and longer times of the electrode contact with solution (Δt) before the beginning of measurements. The effect diminishes after a polarization curve passes through a maximum at E ? 0.5 V. Regularities of the gold dissolution in a solution containing 0.1 M thiourea and 0.5 M H₂SO₄ at given values of c and Δt are studied with use made of the technique of renewing the electrode surface by cutting off a thin surface layer of metal. The discovered regularities are given an explanation which is based on the assumption that the dissolution process is catalyzed by sulfide ions adsorbed on the electrode surface.     

Voltammetric Studies of Cadmium‐ and Zinc‐Containing Metallothioneins at Nafion‐Coated Mercury Thin Film Electrodes

Voltammetric studies of rabbit liver metallothioneins (MTs, containing both Zn and Cd ions) and Zn₇‐MT were carried out at Nafion‐coated mercury film electrodes (NCMFEs). The accumulation of MT molecules into the NCMFEs enhances the voltammetric signals and the electrostatic interaction between the Nafion membrane and MT facilitates facile electron transfer reactions. Two well‐defined redox waves, with reduction potential (E_pc) values at ?0.740 and ?1.173 V, respectively, were observed. The peak at E_pc =?0.740 V is attributable to the reduction of the Cd‐MT complex, whereas that at E_pc=?1.173 V was assigned to the reduction of the Zn‐MT complex. Zn₇‐MT exhibits only one redox wave with E_pc=?1.198 V. The NCMFE was found to be more advantageous than thin mercury film electrode (MFE), because the pristine metal ions in MTs (e.g., Cd²⁺ and/or Zn²⁺) are not significantly replaced by Hg²⁺. The NCMFE is also complementary to Nafion‐coated bismuth film electrode in that it has a greater hydrogen overpotential, which allows the reduction of the Zn‐MT complex to be clearly observed. Moreover, intermetallic compound formation between Cd and Zn appears to be less serious at NCMFEs. Consequently, the amounts of Cd and Zn deposited into the electrode upon the reduction reactions can be quantified more accurately.