Cationic catalysis and hidden negative differential resistance in reduction of radical anion of nitrobenzene

Well-known reduction of nitrobenzene in acetonitrile yields an anion radical, which is further reduced at more negative potentials. The reduction of anion radical is strongly influenced by the nature of tetraalkylammonium salts (tetramethyl- to tetraheptylammonium) used as supporting electrolytes. At low concentration of tetrahexylammonium hexafluorophosphate the anion radical reduction occurs at extremely negative potential, however, traces of alkali metal cations yield a remarkable acceleration effect. At potentials where alkali metal cations are reduced the acceleration ceases. As a result the current-potential curves show negative or hidden negative slope. Electrochemical impedance spectroscopy sensitively indicates the presence of the negative differential resistance (NDR) or the hidden negative differential resistance (HNDR). Oscillatory behavior based on this type of cationic catalysis is currently under investigation.     

Electrochemical investigation of the effects of hydrogen on the stability of the passive film on iron

The effects of hydrogen on the stability of passive films on iron were investigated by electrochemical methods: open circuit potential decay, cathodic galvanostatic reduction, electrochemical impedance spectroscopy, and breakdown potential measurements. The results show that hydrogen decreases the final static open circuit potential, the cathodic charge for reduction and the charge transfer resistance of the passive film, indicating that hydrogen decreases the stability of the passive film. The charge transfer resistance of the passive film formed on the charged specimen does not change with increasing the film formation potentials, suggesting that increasing film formation potentials under hydrogen charging conditions cannot improve the stability of the passive film. Hydrogen decreases the breakdown potential of the passive film, especially at lower chloride ion concentrations, confirming that hydrogen promotes the susceptibility of the passive film on iron to pitting corrosion. The reasons why hydrogen decreases the stability of the passive film were discussed.     

Cathodic reduction of the anodically formed zinc species as a contribution to the study of the potentiodynamic passivation of zinc in alkaline media

The cathodic part of the potentiodynamic curves obtained for upward-facing horizontal 99.9% zinc electrodes in KOH solutions 0.4, 1.0, 2.0 and 3.0 M and sweep rates in the range 1–100 mV s⁻¹ have been systematically analyzed in order to assign the possible species formed and contribute to the study of the potentiodynamic passivation of Zn in alkaline media. The anodic limit of the potentiodynamic cycles was changed and set for significant points of the total curve (between hydrogen and oxygen evolution). Also, the anodic sweep was interrupted at the potentials corresponding to the anodic limit and the cathodic sweep applied immediately from a potential near that of zero current of the cathodic half-cycle. Only two cathodic peaks have been found for the non-interrupted cycles. The assignation of peaks according to the equilibrium potentials of the reduction of the possible species implied, ie Zn(OH)²⁻₄, Zn(OH)₂ and ZnO, is not possible because local pH changes are expected and the zincate concentration near the electrode is unknown. The peak placed at more positive potentials for KOH concentrations 0.4 and 1.0 M is assigned to zincate and that at more negative potentials, to the reduction of the film. Just the opposite assignation has been found for 2.0 and 3.0 M KOH solutions. The experimental results can be interpreted assuming that the product formed at the passivation potential consists of the same chemical species as those corresponding to the first anodic peak, probably Zn(OH)₂ or hydrated ZnO. From calculating the maximum film thickness according to the charge passed and taking into account the recent theoretical analysis made by Chang and Prentice, it is concluded that the direct formation of ZnO on the electrode at the passivation potential as a consequence of local pH changes is not probable.     

Glassy carbon surface effects on the electroreduction of aromatic carbonyl compounds Part III: Vanillin

Voltammetric studies of vanillin reduction in aprotic (DMF) and aqueous media in three different pH ranges on glassy carbon electrodes (GCE's) are presented. The formation and stability of anion radicals and their reactivity towards protonating agents are discussed. On a partially polished or pretreated GCE in DMF as well as on a polished GCE in neutral aqueous media, a new time-dependent surface prewave is noticed. The evidence indicates that this prewave is due to the interaction of acidic functional groups present on the GCE surface with vanillin. In acidic, neutral and alkaline media, the main reduction process occurs at potentials close to the background reduction potential region.     

On the reduction potential of cation-exchanged heteropolyacids (HPAs)

UV-Visible spectroscopy and scanning tunneling microscopy (STM) studies were performed to explore reduction potentials of cation-exchanged Keggin-type heteropolyacid (HPA) catalysts. Absorption band edge and negative differential resistance (NDR) peak voltage of cation-exchanged HPA samples determined by UV-Visible spectroscopy and STM, respectively, were colsely related to their reduction potentials. It was observed that HPAs with higher reduction potentials showed absorption band edges at longer wave lengths and exhibited NDR peak voltages at less negative applied values. The reduction potentials of cation-exchanged HPA catalysts could also be correlated with the electronegativities of counter-cations. Substitution of more electronegative counter-cations increased reduction potentials of the HPAs. The NDR peak voltage and the absorption band edge of HPAs could be utilized as a correlating parameter for their reduction potentials.     

Reduction of nitrogen monoxide to nitrogen at gas diffusion electrodes with noble metal catalysts

The electrochemical reduction of NO in alkaline solutions was investigated at gas diffusion electrodes with various metal (Ru, Rh, lr, Pd and Pt) catalysts at various NO flow rates. Reduction currents are observed at potentials more negative than 0.95 V, which increase with the decrease in potential and also with increasing gas flow rate. The faradaic efficiencies of N2O formation decrease with decreasing NO flow rate and with decrease in potential. The faradaic efficiencies of N2 formation increase with decreasing flow rate and with decrease in potential. The reduction of NO to N2 at a flow rate of 5mlmin–1 occurs selectively at potentials more negative than 0.1V; the faradaic efficiency of N2 formation is approximately 95 at Pd catalysts.Electricity production and NO decomposition can be carried out simultaneously using an H2NO fuel cell reactor. The faradaic efficiency of N2 formation at a flow rate of 5mlmin–1 is approximately 80 at a cell voltage of 0.25 V.     

The electrochemical reduction of Sn(II) at the dropping mercury electrode from aqueous 1 M sulfuric acid and from 0.3 M phenolsulphonic acid and its inhibition by ensa-6

By means of the demodulation technique for the first time the high reduction rate constant of the Sn(II) ion in sulfuric acid is obtained. From the value of the operational transfer coefficient it follows that a following, potential independent “chemical” step is rate determining. On the addition of an inhibitor at positive potentials the transfer of the first electron can be made slow because this process is inhibited much more strongly than the following chemical step. At high concentration of the inhibitor the first electron transfer is rate determining at all potentials. In phenolsulphonic acid as the base electrolyte it appears that an intermediate chemical step is rate controlling together with the following chemical step. The intermediate step could be made rate determining by adding a little of the inhibitor. With a high concentraton of the inhibitor the first electron transfer becomes rate controlling again. Also the reduction of Sn(II) from a practical plating bath is discussed.     

The effect of reduction potential on charge/discharge reactions on porous lead-bismuth electrodes (positives)

A series of discharge experiments were performed from the PbO₂/O₂ region to various reduction potentials using the potential step technique. Two distinct potential ranges were observed, one which occurs at potentials between 1050 and 1100 mV and the second, where there was a much larger output of capacity between 400 and 700 mV. Between these two regions there is a plateau where the relatively small output in capacity during discharge experiments enables almost complete recharging to be effected. The data presented here shows that once the electrode has entered the second reduction region it is virtually impossible to recharge the electrode using this experimental technique.     

Cathodic processes in the leaching and electrochemistry of covellite in mixed sulfate–chloride media

The cathodic processes that occur on a covellite (CuS) surface in mixed sulfate–chloride solutions in the absence and presence of copper(II) ions have been studied using potentiostatic transients and cyclic voltammetry at rotating disk electrodes in the potential range 0.3–0.7 V (versus SHE). This range is relevant to the oxidative leaching of this copper mineral in sulfate and chloride lixiviants. Variations in the concentrations of sulfate and chloride ions had a small effect on the cathodic reduction of covellite in the potential range of 0.5–0.3 V, although the presence of chloride ion resulted in a significant increase in the anodic current on the reverse sweep. On the other hand, addition of copper(II) ions resulted in enhanced cathodic currents and subsequent anodic currents in both sulfate and chloride solutions due to reduction of covellite to an undefined reduced copper sulfide species. Reduction of copper(II) to copper(I) ions becomes the preferred cathodic reaction as the concentration of chloride ions increases, becoming mass transport controlled at a rotating disc electrode at potentials below about 0.4 V. Potentiostatic measurements at potentials negative to the mixed potential in acidic chloride solutions have shown that reduction of copper(II) ions is reversible and have been used to estimate the rate of oxidative dissolution of the mineral which value agrees reasonably well with previously reported leaching rates under similar conditions. Reduction of dissolved oxygen has been found to be very much slower that that of copper(II) ions under ambient conditions.     

Substituent effects on the reduction potentials of benzalacetophenones (chalcones): Improved substituent constants for such correlations

The reduction potentials of a set of 23 monosubstituted and 7 disubstituted benzalacetophenones (chalcones) are linearly correlated considerably better with the σⁿ values of van Bekkum, Verkade, and Wepster than with Hammett σ. Groups were found to exert the same effect upon the reduction potential irrespective of which ring they are located on. The data for monosubstituted benzalacetophenones can be used to predict the reduction potentials of disubstituted derivatives with good accuracy.     

A note on the impedance of reduced PbO2 layers on some lead alloys in sulphuric acid

The impedances of reduced layers of PbO₂ in sulphuric acid are measured at potentials in the range between initial discharge and complete reduction to lead. The electrode behaviour is fairly polarizable when the electrode is remote from the PbSO₄/Pb potential. Near the reversible potential the electrode behaves as a porous electrode under charge-transfer and diffusion control.     

Temperature dependence of two types of dissolution of platinum in acid media. An electrochemical nanogravimetric study

Smooth and platinized platinum electrodes in contact with sulfuric acid solutions were studied using electrochemical quartz crystal nanobalance (EQCN) technique at different temperatures.Two types of dissolution processes have been observed. A platinum loss was detected during the reduction of platinum oxide, the extent of which depends on the positive potential limit and the scan rate, and to a lesser extent on the temperature. The platinum dissolution during the electroreduction of oxide is related either to the mechanical detachment of Pt atoms which were loosely bounded due to the interfacial place exchange of the oxygen and platinum atoms in the oxide region or to the reduction of Pt(IV) formed at higher positive potentials resulting in soluble Pt²⁺ species. At elevated temperatures two competitive processes take place at high positive potentials: a dissolution of platinum and platinum oxide formation. The presence of dissolved platinum in the solution has been detected by two different methods.These phenomena are of importance regarding the long-term stability of proton exchange fuel cells.     

Current efficiency studies for graphite and SnO2-based anodes for the electro-deoxidation of metal oxides

Studies were performed investigating the electrochemical reduction of chromium oxide (Cr₂O₃) by electro-deoxidation by utilising either a graphite anode or a tin oxide (SnO₂) based anode. Potentiostatic electrolysis was performed at 3.0 V for both a graphite and for a SnO₂-based anode, and also 2.0 V for a graphite anode. The cathode reduction purity, anode mass change, anode potential relative to a glassy carbon pseudo-reference and current efficiency were measured and compared. The key observations are that substituting a SnO₂-based anode for a graphite anode led to greater current efficiencies for electro-deoxidation. This was attributed to the lack of contamination of the melt by carbon and the lower cathode potential due to the higher anodic potential when using tin oxide based anodes for the same applied voltage. The current efficiency was also found to decrease with both anode materials when higher anode surface areas or lower current densities were used. Again this was attributed to a decrease in anodic potentials and a corresponding increase in the cathodic potential resulting in a greater number of parasitic reactions occurring at the cathode.     

Electrochemical studies of the inhibition of the cathodic delamination of organically coated galvanised steel by thin conversion films

Scanning Kelvin Probe (SKP) measurements of thin amorphous conversion film coated galvanised steel in combination with current density-potential curves and electrochemical impedance spectroscopy (EIS) were performed with the aim to improve the understanding of electrode potentials at the coating/metal interface and their influence on corrosive de-adhesion. The thin hybrid conversion films contained Zn-phosphates, titanates and also complexing organic compounds and led to an inhibition of the cathodic oxygen reduction and anodic zinc dissolution. In the polymer coated area the conversion film leads to a cathodic shift of the potential as measured by means of the SKP. This cathodic potential shift is explained by the substitution of the n-semiconducting Zn-oxide with an insulating inorganic layer. When the SKP detects the potential of freely corroding iron at a defect, where no protective coating layer is, the interfacial potential for the conversion film coated zinc layer is more negative than the defect potential. This leads to a diminished driving force for an oxygen reduction induced delamination process which is of relevance for the understanding of cut-edge corrosion.     

Electropolymerization of 2‐methacryloyloxy(ethyl) acetoacetate on aluminum using a novel initiation method

Electropolymerization has been used as a method to form polymers on graphite fibers and metals. Most of the previous studies have involved either the use of sulfuric acid as an initiator or direct reduction or oxidation of monomers to form the polymers. In this article, α‐bromoisobutyronitrile (BrIBN) was used as a new electrochemical initiator to form polymer coatings on an aluminum cathode. The reduction of BrIBN on a glassy carbon electrode was examined using cyclic voltammetery. It was found that BrIBN could be reduced to isobutyronitrile radicals at potentials below the reduction potential of water. The reduction behavior of BrIBN was found to be similar in aqueous, semiaqueous, and nonaqueous solutions. 2‐Methacryloyloxy(ethyl) acetoacetate was then electropolymerized on aluminum using the BrIBN as the initiator and lithium perchlorate as a supporting electrolyte. Defect‐free coatings were formed at half‐cell potentials of less than −1.20 V. The effect of various process variables on the polymerization kinetics under potentiostatic conditions is reported. The coating thickness increased with polymerization time, monomer concentration, and initiator concentration. A strong dependence of thickness on monomer concentration was observed. As expected, there was weak dependence on the initiator concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1665–1675, 1999     

Polypyrrole-based electrode coatings switchable electrochemically between the anion- and cation-exchanger states

Dodecylsulphate was incorporated into a polypyrrole matrix during anodic polymerization of pyrrole. The concentration was adjusted such that in the oxidized film about one half of the polypyrrole cationic groups was charge compensated by the sulphate groups from the incorporated dodecylsulphate, the second half by anions from the electrolyte. Upon electrochemical oxidation/reduction, the film is reversibly “switched” between a cation-exchanger (at negative electrode potentials), and an anion exchanger (at more positive potentials) state. The different states of the film are characterized by electrochemical, EDAX, and in particular by Volta-potential measurements. The Donnan potentials determined with the latter techniques as a function of electrode potential and electrolyte concentration were in good agreement with calculated values.     

Nanostructured carbon electrodes for laccase-catalyzed oxygen reduction without added mediators

Reduction of dioxygen catalyzed by laccase was studied at carbon electrodes without any added mediators. On bare glassy carbon electrode (GCE) the catalytic reduction did not take place. However, when the same substrate was decorated with carbon nanotubes or carbon microcrystals the dioxygen reduction started at 0.6 V versus Ag/AgCl, which is close to the formal potential of the laccase used. Four different matrices: lecithin, hydrophobin, Nafion and lipid liquid-crystalline cubic phase were employed for hosting fungal laccase from Cerrena unicolor. The carbon nanotubes and nanoparticles present on the electrode provided electrical connectivity between the electrode and the enzyme active sites. Direct electrochemistry of the enzyme itself was observed in deoxygenated solutions and its catalytic activity towards dioxygen reduction was demonstrated. The stabilities of the hosted enzymes, the reduction potentials and ratios of catalytic to background currents were compared. The boron-doped diamond (BDD) electrodes prepolarized to high anodic potentials exhibited behavior similar to that of nanotube covered GCE pointing to the formation of nanostructures during the anodic pretreatment. BDD is a promising substrate in terms of potential of dioxygen reduction, however the catalytic current densities are not large enough for practical applications, therefore as shown in this paper, it should be additionally decorated with carbon particles being in direct contact with the electrode surface.     

Electrocatalytic carboxylation of chloroacetonitrile at a silver cathode for the synthesis of cyanoacetic acid

The electrocatalytic carboxylation of chloroacetonitrile to cyanoacetic acid performed at silver cathodes was investigated both theoretically and experimentally. Silver exhibits powerful electrocatalytic activities towards the reduction of chloroacetonitrile. In CO₂-saturated CH₃CN, reduction of NCCH₂Cl occurs at potentials that are about 0.7 V more positive than those observed at glassy carbon and gives cyanoacetic acid in good yields. Theoretical considerations on the effect of operative parameters on the performances of the process were confirmed by electrocarboxylation experiments performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivities and Faradic efficiencies higher than 80% were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at proper values of either current density or applied potential.     

Electrochemical studies of pyrite oxidation and reduction using freshly-fractured electrodes and rotating ring-disc electrodes

Oxidation and reduction processes on coal- and mineral-pyrite surfaces have been investigated to better understand the reactions that control the hydrophobicity and flotation behavior of pyrite. The incipient oxidation and reduction reactions were studied using fresh surfaces of pyrite that were created by in situ fracturing electrodes potentiostated at a predetermined potential. Chronoamperometry immediately after fracture and subsequent cyclic voltammetry have established that fresh fracture surfaces of pyrite instantaneously assume a unique potential (referred to as the “stable” potential) at which neither oxidation nor reduction takes place. For Peruvian and Chinese pyrites, the stable potential is −0.28 V (standard hydrogen electrode, SHE) at pH 9.2 and 0 V at pH 4.6. The initial oxidation of pyrite begins at potentials slightly positive of the stable potential and is believed to produce a hydrophobic sulfur-rich species, most likely a polysulfide or metal-deficient sulfide. A rotating ring-disc electrode (RRDE) was employed to study the kinetics and mechanisms of surface reactions on pyrite over moderate potential ranges. Two distinct soluble reduction products (ferrous hydroxide and HS⁻) and one distinct soluble oxidation product (ferrous hydroxide) were observed on pyrite in alkaline solutions. It is concluded that the initial oxidation of pyrite and the oxidation of ferrous to ferric hydroxide occur in a similar potential range. When the electrode is oxidized, e.g. by polishing, prior to experiments, the initial oxidation of pyrite is masked by the oxidation of ferrous hydroxide, making it difficult to study the oxidation of pyrite itself.     

Use of cascade reduction potential for selective precipitation of Au,Cu, and Pb in hydrochloric acid solution

Optimization of reduction potential for electroseparation was studied for the recovery of gold, copper, and lead from acidic solution. A linear sweep voltammetric method enabled us to determine characteristic reduction potentials for each metal and the kinetics of the metal deposition indicated by current-voltage curves. In order to precipitate the metal species sequentially, reduction potentials were examined for the individual and mixed solutions of Au(III), Cu(II), and Pb(II). The three metals were reasonably well isolated from the mixed solutions such as Cu(II)/ Pb(II) and Au(III)/Cu(II)/Pb(II) in the order of the corresponding reduction potentials, in particular, the mass transfer controlled reduction potentials, obtained from linear sweep voltammetry (LSV) measurement.