Electroreduction of nitrate ions on Pt(1 1 1) electrodes modified by copper adatoms

Kinetics and mechanism of nitrate ion reduction on Pt(1 1 1) and Cu-modified Pt(1 1 1) electrodes have been studied by means of cyclic voltammetry, potentiostatic current transient technique and in situ FTIRS in solutions of perchloric and sulphuric acids to elucidate the role of the background anion. Modification of platinum surface with copper adatoms or small amount of 3D-Cu crystallites was performed using potential cycling between 0.05 and 0.3 V in solutions with low concentration of copper ions, this allowed us to vary coverage θ_Cu smoothly. Following desorption of copper during the potential sweep from 0.3 to 1.0 V allowed us to estimate actual coverage of Pt surface with Cu adatoms. Another manner of the modification was also applied: copper was electrochemically deposited at several constant potentials in solutions containing 10⁻⁵ or 10⁻⁴ M Cu²⁺ and 5 mM NaNO₃ with registration of current transients of copper deposition and nitrate reduction.It has been found that nitrate reduction at the Pt(1 1 1) surface modified by copper adatoms in sulphuric acid solutions is hindered as compared to pure platinum due to induced sulphate adsorption at E < 0.3 V. Sulphate blocks the adsorption sites on the platinum surface and/or islands of epitaxial Cu(1 × 1) monolayer thus hindering the adsorption of nitrate anions and their reduction. The extent of inhibition weakly depends on the copper adatom coverage. Deposition of a small amount of bulk copper does not affect noticeably the rate of nitrate reduction.Nitrate reduction on copper-modified Pt(1 1 1) electrodes in perchloric acid solutions occurs much faster as compared to pure platinum. The steady-state currents are higher by 4 and 2 orders of magnitude at the potentials of 0.12 and 0.3 V, respectively. The catalytic effect of copper adatoms is largely caused by the facilitation of nitrate adsorption on the platinum surface near Cu_ad and/or on the islands of the Cu(1 × 1) monolayer (induced nitrate adsorption).Hydrogen adatoms block the adsorption sites on platinum for NO₃⁻ anion adsorption and inhibit reactions of nitrate reduction even at moderate surface coverage.The products of nitrate reduction in sulphuric and perchloric acids are essentially the same (NO and ammonia) irrespective of the presence or absence of Cu on the platinum surface.     

Electrochemical modification of glassy carbon electrode by poly-4-nitroaniline and its application for determination of copper(II)

Electrochemical modification of glassy carbon (GC) electrode by poly-4-nitroaniline (P4NA), electrochemical reduction of P4NA and applicability of electrode modified in this way for determination of copper(II) (Cu(II)) is reported in this study. Electrochemical surface modification was performed by cyclic voltammetry in the potential range between +0.9 V and +1.4 V vs. Ag/Ag⁺ (in 10 mM AgNO₃) at the scan rate of 100 mV/s by 100 cycles in non-aqueous media. In order to provide electrochemical reduction of nitro groups on the P4NA-modified GC electrode surface (P4NA/GC), the cyclic voltammograms inducing/evidencing the reduction of nitro groups were performed in the potential range between −0.1 V and −0.8 V vs. Ag/AgCl/(sat.KCl) at the scan rate of 100 mV/s. The reduced P4NA/GC surfaces (Reduced-P4NA/GC) were treated with aqueous solution of nitrilotriacetic acid. The sensitivity of GC electrode modified in described way towards Cu(II) was investigated in Britton-Robinson buffer solution, pH 5.0. The potentiometric generic pulse technique was applied as innovative electrochemical method for detection of analytical signal. It was shown that GC electrodes modified in here described way will be suitable for the determination of Cu(II) in technological waste water and/or some other solutions containing Cu(II) ions.     

Copper chloride modified copper electrode: Application to electrocatalytic oxidation of methanol

Copper chloride modified copper (CCMC) electrode was prepared as a new electrode. For the preparation of the modified electrode, the polished copper electrode was placed in 0.1 M CuCl₂ solution for 20 s. In this step, a layer of copper (I) chloride was formed at the surface of copper electrode. Then, the electrode was placed in 0.1 M NaOH and the electrode potential was cycled between −250 and 1000 mV (vs. SCE) at a scan rate of 50 mV s⁻¹ for 5 cycles in a cyclic voltammetry regime until a featureless voltammogram was obtained. Surface physical characteristics of the modified electrode were studied by scanning electron micrographs (SEM). Results showed that considerable amounts of microcrystals have been formed on the copper surface during the modification. Surface elemental analysis of electrode were performed by energy dispersive X-ray (EDX) technique. The results showed that in addition to copper and chloride elements, there is also oxygen at the surface of CCMC electrode. This indicates that a layer of (ClCu)₂O was formed at the surface of the modified electrode. The electrocatalytic activity of the modified electrode for the oxidation of methanol, in aqueous basic solution was studied by using cyclic voltammetry. Results showed that, copper chloride modified electrode can improve the activity of Cu towards the oxidation of this small organic molecule, showing the possibility of attaining good electrocatalytic anodes for fuel cells. The modified electrode shows a stable and linear response in the concentration range of 5 × 10⁻³ to 8 × 10⁻² M with a correlation coefficient of 0.9958.     

Electrochemical activity of Geobacter sulfurreducens biofilms on stainless steel anodes

Stainless steel was studied as anode for the biocatalysis of acetate oxidation by biofilms of Geobacter sulfurreducens. Electrodes were individually polarized at different potential in the range −0.20 V to +0.20 V vs. Ag/AgCl either in the same reactor or in different reactors containing acetate as electron donor and no electron acceptor except the working electrode. At +0.20 V vs. Ag/AgCl, the current increased after a 2-day lag period up to maximum current densities around 0.7 A m⁻² and 2.4 A m⁻² with 5 mM and 10 mM acetate, respectively. No current was obtained during chronoamperometry (CA) at potential values lower than 0.00 V vs. Ag/AgCl, while the cyclic voltammetries (CV) that were performed periodically always detected a fast electron transfer, with the oxidation starting around −0.25 V vs. Ag/AgCl. Epifluorescent microscopy showed that the current recorded by chronoamperometry was linked to the biofilm growth on the electrode surface, while CVs were more likely linked to the cells initially adsorbed from the inoculum. A model was proposed to explain the electrochemical behaviour of the biofilm, which appeared to be controlled by the pioneering adherent cells playing the role of “electrochemical gate” between the biofilm and the electrode surface.     

Determination of the kinetic parameters of oxygen reduction on copper using a rotating ring single crystal disk assembly (RRDCu(h k l)E)

The kinetics of the oxygen reduction reaction (orr) on Cu(h k l) surfaces are investigated in perchloric acid and sulfuric acid solutions using rotating ring disk electrode (RRD_Cu(h k l)E). Parameters, such as reaction order, kinetic current, rate constant, Tafel slopes as well as the number of electrons transferred are determined. The variation in the activity and reaction pathway with the crystal faces in different electrolytes is related to the surface characteristics of Cu(h k l) and the structure-sensitive inhibiting effect of the adsorbed anions on their surfaces. In 0.1 M HClO₄, the difference in activity is clearly observed on Cu(h k l) surfaces (Cu(1 0 0) > Cu(1 1 1) although it is relatively small). The higher activity of Cu(1 0 0) arises from its more open characteristics which may facilitate the co-adsorption of O₂. On the other hand, the adsorption of oxygenated species on Cu(1 1 1) at E > −0.35 V induces a 2 e⁻ pathway; while a 4 e⁻ reduction is observed on Cu(1 0 0) in the entire potential region (−0.70 V < E < −0.10 V). In 0.5 M H₂SO₄, the sequence in activity between Cu(1 1 1) and Cu(1 0 0) varies with the potentials, i.e., Cu(1 0 0) is initially more active than Cu(1 1 1) at −0.35 V < E < −0.15 V, however, the reversal in the activity between Cu(1 1 1) and Cu(1 0 0) is observed at more negative potentials (−0.45 V < E < −0.35 V). The desorption of strongly adsorbed (bi)sulfate anions on Cu(1 1 1) induces the 2 e⁻ reduction via peroxide formation, however, a 4 e⁻ reduction is dominant on the Cu(1 0 0) surfaces. The major effect of (bi)sulfate anions and oxygenated species on the orr kinetics and reaction pathway on Cu(h k l) surfaces is the blocking of active copper sites for the adsorption of O₂ molecules.     

All-wet fabrication process for ULSI interconnect technologies

“All-wet process” for fabrication of Cu wiring on a silicon chip was proposed as a novel ultra-large scale integration (ULSI) interconnect technology for integrated circuits (ICs) applications. Electroless-NiB film was deposited on SiO₂/Si substrate modified by self-assembled-monolayer (SAM) activated with PdCl₂. The NiB film formed by this method has highly uniform, with good adhesion to the substrate and with good diffusion barrier characteristics against Cu diffusion. Cu was electrodeposited directly on the electroless NiB film that acted as a seed layer. This was done without any conventional conductive or adhesive layer that is conventionally formed by physical vapor deposition (PDV). The thermal stability of electroless NiB layer as a barrier preventing copper from diffusing into the SiO₂/Si substrate was evaluated by secondary ion mass spectroscopy (SIMS) and sheet resistance measurement at several annealing temperatures. It was confirmed that the electroless NiB film blocked Cu diffusion and kept the layer integrity under annealing temperatures of up to 400 °C for 30 min. The same process of electroless NiB was used for the capping layer that was also formed by “wet process”, as the electroless NiB film deposited selectively onto a surface of Cu wiring was also applicable to a capping layer. We conclude that the proposed process is very promising for sub-100 nm technologies as it offers a variety of desirable properties: it has good step coverage while showing good barrier and seed layer properties.     

Study of the electroreduction of nitrate on copper in alkaline solution

The electrocatalytic activity of a Cu electrode for the electroreduction of nitrate in alkaline medium was investigated by linear sweep voltammetry at stationary and rotating disc electrodes. Nitrate-reduction products generated upon prolonged electrolyses at different potentials were quantified. In addition, adsorption phenomena associated with the nitrate electroreduction process were characterized by electrochemical quartz crystal microbalance (EQCM) experiments. This data revealed that nitrate electroreduction process strongly depends on the applied potential. Firstly, at ca. −0.9 V vs. Hg/HgO, the electroreduction of adsorbed nitrate anions to nitrite anions was identified as the rate-determining step of the nitrate electroreduction process. Between −0.9 and −1.1 V, nitrite is reduced to hydroxylamine. However, during long-term electrolyses, hydroxylamine is not detected and presumably because it is rapidly reduced to ammonia. At potential more negative than −1.1 V, nitrite is reduced to ammonia. At ca. −1.45 V, i.e. just before the hydrogen evolution reaction, the abrupt decrease of the cathodic current is due to the electrode poisoning by adsorbed hydrogen. In addition, during the first minutes of nitrate electrolysis, a decrease of the copper electrode activity was observed at the three investigated potentials (−0.9, −1.1 and −1.4 V). From polarization and EQCM measurements, this deactivation was attributed to the adsorption of nitrate-reduction products, blocking the electrode surface and slowing down the nitrate electroreduction rate. However, it was demonstrated that the Cu electrode can be reactivated by the periodic application of a square wave potential pulse at −0.5 V, which causes the desorption of poisoning species.     

Antagonistic effects of copper on the electrochemical performance of LiFePO4

In the last few years, several strategies towards boosting the electrochemical performance of LiFePO₄ cathodes have been envisaged. Copper addition to the phosphate seems to be a simple, inexpensive method for this purpose. However, it has a serious drawback: at voltages slightly higher than that required for lithium extraction from LiFePO₄, the copper is oxidized to either Cu(I) or Cu(II) with partial decomposition of the electrolyte. XRD patterns are consistent with the disappearance of copper from pristine composites upon charging at up to 4.0 V. Moreover, a copper deposit is formed on the lithium surface in the discharged state that creates a barrier hindering the release of Li ion from the electrode. Therefore, copper electroactivity strongly influences the capacity and cycling life of the cell.     

Spectroelectrochemical characterisation of copper salen-based polymer-modified electrodes

Electrogenerated polymers based on copper salen-type complexes were characterised electrochemically and by in situ UV-vis and ex situ EPR spectroscopy. The films, poly[Cu(salen)] and poly[Cu(saltMe)], exhibit reversible oxidative electrochemical behaviour in a wide potential range (0.0-1.5 V). Different regimes for charge transport behaviour are accessed by manipulation of film thickness and experimental time scale: thin films (surface concentration, Γ < ca. 80 nmol cm⁻²) show thin-layer/surface behaviour in the scan rate range used (0.020-2.0 V s⁻¹), whereas thicker polymers (Γ > ca. 90 nmol cm⁻²) exhibit a changeover from thin-layer to diffusion control regime at a critical scan rate that depends on polymer and film thickness: 0.15-0.20 V s⁻¹ for poly[Cu(salen)], 90 < Γ < 130 nmol cm⁻² and 0.20-0.30 V s⁻¹ for poly[Cu(saltMe)], 170 < Γ < 230 nmol cm⁻².UV-vis and EPR spectroscopies have allowed the characterisation of electronic states in the reduced and oxidised forms. The role of the copper atom during film oxidation was probed by combining UV-vis data with EPR on copolymers of the copper and nickel complexes. Data from both techniques are consistent and indicate that polymerisation and redox switching are associated with ligand-based processes. EPR of Ni-doped Cu polymers provided evidence for the non-involvement of the metal centre in polymer oxidation; like the analogous nickel polymers, copper polymers behave like delocalised π-system (‘conducting’) rather than discrete site (‘redox’) polymers.     

Electrodeposition of Co-Ni and Co-Ni-Cu systems in sulphate-citrate medium

Electrodeposition of Co-Ni and Co-Ni-Cu alloys was performed in a sulphate-citrate medium. Experimental electrodeposition parameters (pH, cobalt(II), nickel(II) and citrate concentrations) were varied in order to analyse their influence on the deposition. Anomalous Co-Ni codeposition occured in the citrate medium. High [Ni(II)]/[Co(II)] ratios (above 5) were suitable for the preparation of homogeneous magnetic Co-rich Co-Ni deposits of hexagonal close-packed (hcp) structure or face centred cubic (fcc) structure as a function of the deposition potential.The presence of very low copper(II) concentrations (<10⁻² mol dm⁻³) in the nickel-cobalt bath makes it possible to incorporate copper in the deposits in amounts ranging from 5 to 60% Cu, although uniform deposits are obtained only for low copper percentages. These ternary deposits are solid solutions with fcc structure and magnetic behaviour both dependent on the deposition potential.     

Electrochemical formation of carbon nano-powders with various porosities in molten alkali carbonates

The electrochemical reduction of molten Li-Na-K carbonates at the eutectic composition was (43.5/31.5/25 mol%) performed in the range 450-700 °C. The analysis of the electrochemical mechanism was done by cyclic voltammetry with an inert vitreous carbon electrode. “Quasi-spherical” carbonaceous particles were obtained with average diameter comprised between 30 and 50 nm. The specific surface area as well as the crystallinity and morphology of the powders were strongly influenced by the operating conditions, i.e. potential deposition, temperature of the molten carbonates, temperature of the drying process after washing. The carbon prepared in our experimental conditions contains micro-, meso- and macroporisty. The proportion of each one is strongly dependent on the operating deposition conditions. The highest specific surface area value (1315 m² g⁻¹) was obtained with carbon powder deposited at 450 °C for an applied potential of −6 V and dried at 600 °C under vacuum after washing.     

Potassium sorbate solutions as copper chemical mechanical planarization (CMP) based slurries

Copper depassivation and repassivation characteristics in potassium sorbate solutions, subsequent to mechanical abrading are reported. The identification of copper repassivation kinetics obtained subsequent to mechanical damage of copper protective films formed in sorbate based solutions is discussed. The repassivation rate of copper in sorbate based solutions was measured by means of a slurryjet system capable of measuring single particle impingments on microelectrodes. Copper repassivation rates measured by this slurryjet system in sulfate solutions containing 10 g L⁻¹ potassium sorbate were found to be in the range of 0.5-1.5 ms. An increase in the potassium sorbate concentration leads to a decrease in copper repassivation time at potentials ranging from 200 to 600 mV_Ag/AgCl. The impingement angle between the copper surface and a single abrasive particle has no impact on copper repassivation time nor peak current (I_max) values. XPS studies revealed that copper passivation in potassium based solution was due to the formation of a thin film which is constituted of: Cu₂O, Cu(OH)₂ and Cu(II)-sorbate, while copper(II)-sorbate is mainly present at the top levels of the passive film. It is therefore recommended that the use of potassium sorbate as a passivating component in conjunction with the addition of strong oxidizing agents in chemical mechanical planarization (CMP) slurry design should be considered.     

Electrochemical characterization of chemical species formed during the electrochemical treatment of chalcopyrite in sulfuric acid

The dissolution mechanism of chalcopyrite, and the potential range in which its passivation phenomenon takes place, were studied on carbon paste electrodes with chalcopyrite (99.46% purity, +300 mesh, 53 μm size) (CPE-CP) in 1.7 mol/dm³ H₂SO₄. A sequence of anodic potential pulses was applied to the CPE-CP to characterize its electrochemical behavior. Copper ions, dissolved by the potential pulses, were determined using a mercury film electrode (MFE) and the anodic stripping voltammetry (ASV) on a vitreous carbon disk. In addition, the modified surface of CPE-CP was characterized, before and after the potential pulses, by cyclic voltammetry (CV). The characterization of the final surface state of each electrochemically modified CPE-CP and the amount of dissolved copper showed five potential regions where the chalcopyrite dissolution mechanism changed. The initial dissolution occurs at 0.615 V ≤ E_anod < 1.015 V versus SHE forming a non-stoichiometric polysulfide (Cu_1−rFe_1−sS_2−t). The absence of copper ions in the solution indicates a passive sulfide. However, at 1.015 V ≤ E_anod < 1.085 V versus SHE, the passive product decomposes forming porous layers of non-stoichiometric polysulfide (Cu_1−xFe_1−yS_2−z) that allow the diffusional transport of charged species and the dissolution of the mineral. In the region of 1.085 V ≤ E_anod < 1.165 V versus SHE, formation covellite (CuS) was identified. At E > 1.165 V versus SHE, CuS is unstable and gives rise to complete dissolution of the chalcopyrite. Due to the experimental conditions, the mineral dissolution is inhibited by possible jarosite precipitation.     

Electrochemical sensor for sulfite determination based on a nanostructured copper-salen film modified electrode

The electrochemical preparation described herein involved the electrocatalytic oxidation of sulfite on a platinum electrode modified with nanostructured copper salen (salen = N,N′-ethylenebis(salicylideneiminato)) polymer films. The complex was prepared and electropolymerized at a platinum electrode in a 0.1 mol L⁻¹ solution of tetrabutylammonium perchlorate in acetonitrile by cyclic voltammetry between 0 and 1.4 V vs. SCE. After cycling the modified electrode in a 0.50 mol L⁻¹ KCl solution, the estimated surface concentration was found to be equal to 2.2 × 10⁻⁹ mol cm⁻². This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the copper(II)/copper(III) couple. The potential peaks of the modified electrode in the electrolyte solution (aqueous) containing the different anions increase with the decrease of the ionic radius, demonstrating that the counter-ions influence the voltammetric behavior of the sensor. The potential peak was found to be linearly dependent upon the ratio [ionic charge]/[ionic radius]. The oxidation of the sulfite anion was performed at the platinum electrode at +0.9 V vs. SCE. However, a significant decrease in the overpotential (+0.45 V) was obtained while using the sensor, which minimized the effect of oxidizable interferences. A plot of the anodic current vs. the sulfite concentration for chronoamperometry (potential fixed = +0.45 V) at the sensor was linear in the 4.0 × 10⁻⁶ to 6.9 × 10⁻⁵ mol L⁻¹ concentration range and the concentration limit was 1.2 × 10⁻⁶ mol L⁻¹. The reaction order with respect to sulfite was determined by the slope of the logarithm of the current vs. the logarithm of the sulfite concentration.     

Embedded space charge in porous alumina films formed in phosphoric acid

The embedded charge in the barrier layers of porous alumina, formed potentiostatically in phosphoric acid was studied as a function of anodizing voltage (30-57 V) and bath temperature (18 and 21 °C). For that, the polarization measurements of as-grown and annealed alumina/Al samples were conducted in the same anodizing bath by anodic potential sweep at a scan rate of 2.6 V/min. The plane capacitor model was used for the assessment of the charge density in the barrier layers of as-grown porous alumina. For the barrier layers of films formed at 18 °C this value equals to 0.747 μC cm⁻² and does not depend on the anodizing voltage. Increase in electrolyte temperature rises the embedded charge density. Polarization measurements carried out in this paper clearly present that the barriers of phosphoric acid films grown at the anodizing voltages lower than 39 V contain a layer of virtual cathode while at higher voltages this layer disappers. The obtained results allow speaking about promising opportunities of potentiodynamic polarization measurements of alumina films in the same anodizing solution before and after annealing for the studies of charges embedded within the alumina barriers and for the regularities of ion transport.     

An in situ scanning tunneling microscopic study of electrodeposition of bismuth on Au(1 1 1) in a 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid: Precursor adsorption and underpotential deposition

In this article, the electrodeposition of Bi on Au(1 1 1) surface in the underpotential region in BMIBF₄ ionic liquid containing BiCl₃ is studied by cyclic voltammetry and in situ scanning tunneling microscopy (STM). The cyclic voltammogram shows several cathodic and anodic peaks associated with underpotential deposition (UPD) of Bi and dissolution of the UPD deposit, respectively, in the potential region between −0.38 and −0.7 V versus Pt quasi-reference electrode. In situ STM results indicate there is a BiCl₃ precursor adsorption stage prior to the Bi UPD. The adsorption of BiCl₃ leads to the formation of unique hexagonal and trigonal supramolecular assembly with a Au(1 1 1)(10 × 10) structure. The initial stage of Bi UPD proceeds with the formation of Au(1 1 1)(7 × 7) R21.8° adlayer structure composed of Bi trigonal clusters at −0.5 V. A structural transformation occurred at −0.6 V resulting in a unique “zipper-like” double-chain pattern composed of well-aligned Bi trigonal clusters which can be denoted by Au(1 1 1)(5 × 25√3/3) structural model. The trigonal clusters composed of six Bi atoms seem to be the main characteristic elemental units of Bi UPD adlayer regardless of underpotential shift. These features are dramatically different from those observed in Bi(III)-containing acidic aqueous solutions as well as in chloroaluminated ionic liquid, but are similar to those of Sb UPD in BMIBF₄ ionic liquid, which reveals profound solvent effects on the electrodeposition of semimetals.     

Fabrication of Pd-Ni alloy nanowire arrays on HOPG surface by electrodeposition

Pd-Ni alloy nanowires with diameters 50-300 nm and lengths of over 250 μm have been obtained by electrochemical step edge decoration (ESED). The fabrication by ESED is accomplished on highly oriented pyrolytic graphite by applying three potential pulses in succession: an oxidizing “activation” pulse, a reducing “nucleation” pulse, and a reducing “growth” pulse. The alloy composition is controlled by adjusting the ion concentration ratio of palladium and nickel, and the deposition processes. The scanning electron microscopy (SEM) images reveal that the alloy nanowires fabricated by this procedure are separate, parallel, and continuous. The composition of alloy nanowires can be controlled in the range of 8-15 wt.% Ni when the ion concentration ratio of palladium and nickel is 7:3 in the solution containing 70 mmol dm⁻³ Pd(NH₃)₄Cl₂. The reaction mechanism involves nucleation at potential of −1.1 V_SCE to −2.0 V_SCE and growth at potential of −0.3 V_SCE to −0.5 V_SCE.     

Copper electrodeposition on pyrolytic graphite electrodes: Effect of the copper salt on the electrodeposition process

The electrodeposition of copper on pyrolytic graphite from CuSO₄ or Cu(NO₃)₂ in a 1.8 M H₂SO₄ aqueous solution was investigated. The Cu deposits were formed potentiostatically and characterized by electrochemical methods, scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopy. It was found that the deposition of copper in the presence of CuSO₄ induced the codeposition of sulfate anions. In addition, electrochemical quartz crystal microbalance revealed that the increase of the Cu mass was higher than expected from Faraday's law with the CuSO₄/H₂SO₄ solution. These results confirmed the specific adsorption of anions during the Cu deposition. On the other hand, the use of Cu(NO₃)₂ resulted in a non-contaminated surface with different surface morphologies. The Cu nuclei size, the population density and the surface coverage were monitored as a function of the deposition potential. From the analysis of the chronoamperometric curves, the nucleation kinetics was studied by using various theoretical models. Independently of the Cu source, the nucleation mechanism follows a three-dimensional (3D) process. Copper nucleates according to an instantaneous mode when the deposition potential is more negative than −300 mV versus Ag/AgCl, while the nucleation was interpreted in terms of a progressive mode at −150 mV. The nuclei population densities were also determined by using two common fitting models for 3D nucleation and growth (Scharifker-Mostany and Mirkin-Nilov-Heerman-Tarallo). Their values are reported here as a function of the deposition potential.     

Surface characterization by X-ray photoelectron spectroscopy and cyclic voltammetry of products formed during the potentiostatic reduction of chalcopyrite

Surface characterization of the transient products that precede chalcocite formation during chalcopyrite reduction was carried out. The experimental strategy employed in the present work consisted of the application of different potential pulses (fixed energetic conditions) on the surface of chalcopyrite electrodes in 1.7 M H₂SO₄. The chemical products formed at different potential pulses were characterized by cyclic voltammetry (CV) and XPS. Each electrogenerated species presented a specific voltammetric behavior and an XPS spectrum, in which the values of principal photoelectronic peak bond energies for Cu 2p_3/2, Fe 2p_3/2 and S 2p_3/2 and the atomic concentrations were considered. Several potential intervals could be identified: in 0.115 ≥ E_cat ≥ −0.085 V vs. SHE, an intermediate copper sulfide is formed whose composition is between those of chalcopyrite and bornite, such as talnakhite. The reduction of this product occurs slowly, giving bornite at potentials less than −0.085 V. In the applied potential region −0.085 ≥ E_cat > −0.185 V, the bornite gradually decomposes causing the incomplete conversion to chalcocite. In the potential interval −0.185 > E_cat ≥ −0.285 V, energetic conditions are large enough to allow the immediate decomposition of bornite, forming chalcocite in a more quantitative manner.     

Oxygen and hydrogen peroxide reduction catalyses in neutral aqueous media using copper ion loaded glassy carbon electrode electrolyzed in ammonium carbamate solution

An aminated glassy carbon electrode (AGCE) can be obtained by the electrode oxidation of glassy carbon electrode in ammonium carbamate solution. In the cyclic voltammetric experiments, the electrode reduction of the dissolved oxygen began from −0.15 V vs. Ag/AgCl in neutral aqueous media when the aminated glassy carbon electrode was used as a working electrode although it began from −0.40 V vs. Ag/AgCl when a polished GCE was used. The nitrogen containing groups introduced by the electrode oxidation of carbamic acid must be related with the acceleration of the electron transfer rate of oxygen. Moreover, the new reduction wave of the dissolved oxygen appeared at +0.15 V vs. Ag/AgCl when copper (II) ion was coordinated to AGCE surface. This reduction potential of oxygen coincided with that of copper (II) ion and this fact suggests that the coordinated copper ion to the aminated carbon surface works as a redox mediator of oxygen. The reduction product of oxygen was monitored by rotating platinum ring - aminated glassy carbon disk electrode, and it was found that most of oxygen was reduced to water in a potential range negative than −0.4 V vs. Ag/AgCl. By using AGCE, it was recognized that the catalytic reduction of hydrogen peroxide was also taken place as well as oxygen reduction.