Evolution of an iron passive film in a borate buffer solution (pH 8.4)

The evolution under open-circuit conditions of iron passive films formed at 0.8 V_SCE in a borate buffer solution at pH 8.4 was investigated with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. The composition of the freshly formed passive film as determined by X-ray photoelectron spectroscopy (XPS) was found to be in agreement with a bilayer model, where the inner layer is composed mainly of iron oxide and the outer layer consists of a hydrated material. Results of XPS measurements also showed that the open-circuit breakdown of passive films was consistent with a reductive dissolution mechanism. When the iron electrode reached an intermediate stage in the open-circuit potential decay (approximately −0.3 V_SCE), the oxide film, containing both Fe(II) and Fe(III), was still protective. The impedance response in this stage exhibited a mixed control by charge transfer at the metal/film and film/solution interfaces and diffusion of point defects through the film. At the final stage of the open-circuit potential decay (approximately −0.7 V_SCE), the oxide film was very thin, and the ratio of Fe³⁺/Fe²⁺ and O²⁻/OH⁻ had decreased significantly. The impedance response also exhibited a mixed charge-transfer–diffusion control, but the diffusion process was related to transport of species in the electrolyte solution resulting from dissolution of the oxide film.     

Electrochemical studies on Zn deposition and dissolution in sulphate electrolyte

The electrochemical deposition and dissolution of Zn on Pt electrode in sulphate electrolyte was investigated by electrochemical methods in an attempt to contribute to the better understanding of the more complex Zn–Cr alloy electrodeposition process. A decrease of the Zn electrolyte pH (from 5.4 to 1.0) so as to minimise/avoid the formation of hydroxo-products of Cr in the electrolyte for deposition of alloy coatings decreases the current efficiency for the Zn reaction, but the rate of the cathode reaction increases significantly due to intense hydrogen evolution. The results of the investigations in Zn electrolytes with pH 1.0–1.6 indicate that Zn bulk deposition is preceded by hydrogen evolution, stepwise Zn underpotential deposition (UPD) and formation of a Zn–Pt alloy. Hydrogen evolution from H₂O starts in the potential range of Zn bulk deposition. Data obtained from the electrochemical quartz crystal microbalance (EQCM) measurements support the assumption that electrochemical deposition of Zn proceeds at potentials more positive than the reversible potential of Zn. Anodic potentiodynamic curves for galvanostatically and potentiostatically deposited Zn layers provide indirect evidence about the dissolution of Zn from an alloy with the Pt substrate. The presumed potential of co-deposition of Cr (−1.9 V vs. Hg/Hg₂SO₄) is reached at a current density of about 300 mA cm⁻².     

Anode-supported solid oxide fuel cell with electrophoretic deposition-derived electrolyte operated under single-chamber conditions and a methane–air mixture

In this study, samaria-doped ceria (Sm_0.2Ce_0.8O_1.9, SDC) thin film is deposited on the Ni-SDC support by employing the electrophoretic deposition technique. Various factors are considered for the deposition of SDC films. The corresponding microstructure of the deposited SDC film is examined and correlated to the electrochemical performance as a single-chamber solid oxide fuel cell (sc-SOFC). It is found that the microstructure of the SDC film mainly relates to the particle size of SDC. After heat treatment, highly dense SDC film is obtained with the deposition condition of 5 g L⁻¹ of the SDC suspension (average grain size of SDC, 248 nm), 60 V as the applied potential, and the deposition time of 1 min (18 μm in thickness). For the Ni-SDC/SDC/SSC cell, an open circuit potential of 0.92 V and peak power density of 155 mW cm⁻² can be obtained at the furnace temperature of 500 °C.     

Formation of cuprous oxide layers in Cu(II) solutions containing gluconic acid

In accordance with thermodynamic analysis, cuprous oxide layers are formed spontaneously in the Cu|Cu(II), gluconic acid system at pH > 3.7 under open-circuit conditions. A current peak of Cu₂O reduction is observed on cathodic voltammograms at ca −0.7 V, its height being dependent on the exposure time. The analysis of the charge transferred in this region yields the rate of Cu₂O formation equal to 1.25 × 10⁻¹⁰ mol cm⁻² s⁻¹. The light perturbation of Cu electrode under open-circuit conditions results in the generation of a negative photopotential, which is indicative of n-type conductivity. The threshold wavelength is equal to ∼590 nm and is consistent with a band gap of ∼2.1 eV. Anodic photocurrents, which are observed near the open-circuit potential, decrease with cathodic polarization and change their sign at ∼0.05 V. Analysis of impedance data was performed, invoking the equivalent circuit that accounts for the two-step charge transfer. In the presence of Cu₂O, some retardation of Cu(II) reduction was found to occur with a slight increase in the admittance of the double layer. The suggestion has been made that oxide layers formed in Cu(II) gluconate solutions cannot be compact and uniformly distributed over the entire electrode surface. Relevant investigations of surface morphology support this conclusion.     

TOF-SIMS depth profiling and element mapping on oxidized AlCrVN hard coatings

V-alloyed AlCrN hard coatings were deposited on silicon wafers (Si (100)) by reactive arc evaporation in a commercial coating system at 500 °C for 10 min, resulting in a coating thickness of ∼500 nm. The chemical composition of the stoichiometric coatings is constant at approximately Al_0.70Cr_0.05V_0.25N regardless of the applied bias voltage during deposition. Coatings synthesized at a low bias of −40 V show a dual-phase structure (hexagonal close-packed and face-centered cubic (fcc)), whereas coatings deposited at a high bias of −150 V have a metastable single-phase structure (face-centered cubic). All samples were oxidized for 15 min under 20 mbar O₂ atmosphere and at four different temperatures (550, 600, 650, and 700 °C). The oxidized coatings were subject to depth profiling and element mapping by a time of flight secondary ion mass spectrometry instrument, equipped with a Bi-cluster analysis gun and Cs⁺-sputter gun. The evaluation of the in-depth distribution of several elements and species points out distinctive differences in the oxidation behavior of the two different coatings, whereas element mapping shows the formation of islands made of oxidized vanadium and aluminum species as the top-most layer of the single-phase (fcc) coating at temperatures above 650 °C.     

Electropolymerization of <Emphasis Type="Italic">trans</Emphasis>-[RuCl<Subscript>2</Subscript>(vpy)<Subscript>4</Subscript>] complex—EQCM and Raman studies

The electropolymerization of trans-[RuCl₂(vpy)₄] (vpy=4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) technique, and Raman spectroscopy. Cyclic voltammetry of the monomer at a microelectrode shows the typical Ru(III/II) and Ru(IV/III) waves, together with the vinyl reduction waves at −1.5 and −2.45 V and adsorption wave at −0.8 V. Electrodeposition on EQCM technique performed under potential cycling between −0.9 and −2.0 V revealed that the polymerization proceeded well in advance of the vinyl reduction waves. At potentials more positive than −0.9 V, soluble oligomers were deposited irreversibly on the electrode during the oxidative sweep. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. In contrast, potentiostatic growth of the polymer at −1.6 V was slower because the oligomeric material was lost completely from the electrode. Unreacted vinyl groups were detected by in situ Raman spectroscopy for films grown at −0.7, −0.9, and −1.6 V but were absent when the polymerization was carried out at −2.9 V vs Ag/Ag⁺.     

CuInSe2 thin-film deposition on flexible plastic substrate: electrolyte recirculation rate and deposition potential effects

Copper indium diselenide (CuInSe₂; CIS) layer was electrolytically plated from an aqueous medium at room temperature onto electroless nickel deposited on flexible plastic (Kapton). The CIS depositions were carried out under constant deposition potentials (−0.5 to −1.1 V vs. Ag/AgCl) and at various electrolyte flow rates (0.3 to 1.5 ml/s) under constant applied current. The resulting thin films were characterized using atomic force microscopy, energy-dispersive X-ray spectroscopy, environmental scanning electron microscopy, and X-ray diffraction. The surface morphology and the atomic composition of the deposited CIS film were found to be influenced by the deposition potential under potential control and the electrolyte recirculation rate under current control. Low electrolyte flow rates under constant current control and high cathodic deposition potential under voltage control favor the deposition of indium. CIS films of uniform deposit, smoother surfaces, and with better adhesion properties are favored by moderate electrolyte recirculation rate. At a current density of 0.6 mA/cm², the electrolyte recirculation rate required to achieve ideal CIS atomic composition was found to be 1.0 ml/s in such a setting. The crystallinity of the film improved after annealing for 2 h at 390 °C under argon atmosphere.     

Effect of ionic conductivity of a PAN–PC–LiClO<Subscript>4</Subscript> solid polymeric electrolyte on the performance of a TiO<Subscript>2</Subscript> photoelectrochemical cell

A nanoparticle TiO₂ solid-state photoelectrochemical cell has been fabricated. The effect of ionic conductivity of a solid electrolyte of polyacrylonitrile (PAN)–propylene carbonate (PC)–lithium perchlorate (LiClO₄) on the performance of a photoelectrochemical cell of indium tin oxide (ITO)/TiO₂/PAN–PC–LiClO₄/graphite has been investigated. A nanoparticle TiO₂ film was deposited onto ITO-covered glass substrate by controlled hydrolysis technique. A solid electrolyte of PAN–LiClO₄ with PC plasticizer prepared by solution casting technique was used as a redox couple medium. The room temperature conductivity of the electrolyte was determined by AC impedance spectroscopy technique. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows a photovoltaic effect under illumination. The short-circuit current density, J _sc, and open-circuit voltage, V _oc, vary with the conductivity of the electrolyte. The highest J _sc of 2.82 μA cm⁻² and V _oc of 0.56 V were obtained at the conductivity of 4.2 × 10⁻⁴ Scm⁻¹ and at the intensity of 100 mW cm⁻².     

Dissolution behavior of anodic oxide films formed in sulfanic acid on aluminum

Chemical dissolution of the barrier layer of porous oxide films formed on an aluminum foil (99.5% purity) in 1.5 M sulfanic acid after immersion in a 2 mol dm⁻³ sulphuric acid at 50 °C was studied. The barrier layer thickness before and after dissolution was determined using a re-anodizing technique. Re-anodizing was conducted in 0.5 mol dm⁻³ H³BO³/0.05 mol dm⁻³ Na²B⁴O⁷ solution. We found that the change in the porous oxide growth mechanism was observed at the anodizing voltage of 30 V. Taking into account this result chemical dissolution behaviour of the barrier layer of porous films formed at 20 V and 36 V and also the influence of annealing of oxide films at 200 °C were studied. We showed the interplay between the dissolution rates and charge distribution across the barrier layer. We conclude that the outer and middle layers have negative space charges and the inner layer has positive space charges.     

Feasibility studies on the electrochemical recovery of fission platinoids from high-level liquid waste

The electrochemical behavior of ruthenium(III) and rhodium(III) in nitric acid medium has been studied at platinum and stainless steel electrodes by cyclic voltammetry. The cyclic voltammograms consisted of surge in cathodic current occurring at potentials of −0.13 V (Vs. Pd) and −0.15 V (Vs. Pd), which culminates into peaks at −0.47 V and −0.5 V due to the reductions of Ru(III) and Rh(III) to their metallic forms, respectively. Electrodeposition was carried out at stainless steel electrode and unlike palladium, the recovery of ruthenium and rhodium was limited to ~4% and ~14%, respectively. However, a different scenario was observed in case of electrodeposition from a ternary solution containing all these platinum metals. Ruthenium and rhodium deposited underpotentially in the presence of palladium and the recovery of ~20% and ~5% was observed for ruthenium and rhodium, respectively. Evolution of RuO₄ at the anode and deposition of RuO₂ in the anodic side was observed in all cases during electrolysis of ruthenium(III) containing solutions.     

Specific adsorption of anions in the course of underpotential and bulk depositions and alloy formation of cadmium on a smooth gold support in acid medium

 The specific adsorption of ³⁶Cl-labelled Cl⁻ ions and ³⁵S-labelled HSO₄ ⁻ ions was studied in 1 mol dm⁻³ HClO₄ supporting electrolyte in the presence of Cd²⁺ ions at a gold support over a wide potential range corresponding to electrodeposition, alloy formation, underpotential deposition of Cd species and existence of an adatom-free surface. The distinct sections in the potential dependence of the adsorption of anions together with the potential versus time curves obtained under open circuit conditions reflect the changes in the state of the electrode surface, the dissolution of the bulk Cd phase and the slow elimination of Cd species from the Cd/Au alloy. Received: 16 March 1999 / Accepted: 5 May 1999     

Determination of hemoglobin at a novel NH2/ITO ion implantation modified electrode

A novel electrode was prepared by implanting NH₂ ⁺ into an ITO film (NH₂/ITO). Gold nanoparticles were deposited on the surface of NH₂/ITO electrode. The NH₂/ITO and Au/NH₂/ITO electrodes were used to determine hemoglobin (Hb) immobilized on the electrodes surfaces. The relationship of the reductive peak current value of Hb among different electrodes was: Hb/ITO:Hb/Au/ITO:Hb/NH₂/ITO:Hb/Au/NH₂/ITO=1:1.5:2:4. The linkage between the –NH₂ implanted into ITO film and the –COOH of Hb was recognized to be the reason for the increase of active Hb coverage on NH₂/ITO electrode compared with the ITO electrode. Increase of active Hb coverage on Au/NH₂/ITO compared with Au/ITO was attributed to the different amount of gold nanoparticles deposited. The determination of Hb at an Au/NH₂/ITO electrode was optimized. Calibration curve was obtained over the range of 1.0 × 10⁻⁸ – 1.0 × 10⁻⁶ mol · L⁻¹ with a detection limit of 1.0 × 10⁻⁸ mol · L⁻¹. Results showed that the novel NH₂/ITO and Au/NH₂/ITO electrodes exhibited good stability, reproducibility besides better electrochemical performance. Correspondence: Jing Bo Hu, Department of Chemistry, Beijing Normal University, Beijing 100875, China     

Preparation and electrocatalytic performance of Fe–N–C for electroreduction of H2O2

Fe–N–C catalysts were prepared through metal-assisted polymerization method. Effects of carbon treatment, Fe loading, nitrogen source, and calcination temperature on the catalytic performance of the Fe–N–C for H₂O₂ electroreduction were measured by voltammetry and chronoamperometry. The Fe–N–C catalyst shows optimal performance when prepared with pretreated active carbon, 0.2 wt.% Fe, paranitroaniline (4-NA) and one-time calcination. The Fe–N–C catalyst displayed good performance and stability for electroreduction of H₂O₂ in alkaline solution. An Al–H₂O₂ semi-fuel cell was set up with Fe–N–C catalyst as cathode and Al as anode. The cell exhibits an open-circuit voltage of 1.3 V and its power density reached 51.4 mW cm⁻² at 65 mA cm⁻².     

Electrochemical modification of Bi2S3 coatings in a nickel plating electrolyte

The electrochemical behavior of Bi₂S₃ coatings in Watts nickel plating electrolyte was investigated using the cyclic voltammetry, electrochemical quartz crystal microbalance, X-ray diffraction, and energy dispersive X-ray analysis methods. During the bismuth sulfide coating reduction in Watts background electrolyte in the potential region from −0.4 to −0.6 V, the Bi₂S₃ and Bi(III) oxygen compounds are reduced to metallic Bi, and the decrease in coating mass is related to the transfer of S²⁻ ions from the electrode surface. When the bismuth sulfide coating is reduced in Watts nickel plating electrolyte, the observed increase in coating mass in the potential region −0.1 to −0.4 V is conditioned by Ni²⁺ ions reduction before the bulk deposition of Ni, initiated by Bi₂S₃. In this potential region, the reduction of Bi(III) oxygen compounds can occur. After the treatment of as-deposited bismuth sulfide coating in nickel plating electrolyte at E = −0.3 V, the sheet resistance of the layer decreases from 10¹³ to 500–700 Ω cm. A metal-rich mixed sulfide Ni₃Bi₂S₂–parkerite is obtained when as-deposited bismuth sulfide coating is treated in Watts nickel plating electrolyte at a potential close to the equilibrium potential of the Ni/Ni²⁺ system and then annealed at temperatures higher than 120 °C.     

Comparative study of electrolessly deposited Pd/Ag films onto p-silicon (100)-activated seed layers of Ag and Pd

Pd/Ag films were electrolessly deposited onto p-silicon (100)-activated seed layers of Ag and Pd, respectively, in the solution of 0.005 mol l⁻¹ AgNO₃ + 0.005 mol l⁻¹ PdCl₂ + 4.5 mol l⁻¹ NH₃ + 0.16 mol l⁻¹ Na₂EDTA+0.1 mol l⁻¹ NH₂NH₂ (pH 10.5) at room temperature. The morphology and composition of the films were studied comparatively by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Cathodic polarization curves for hydrogen evolution were recorded in 0.5-mol l⁻¹ H₂SO₄ without illumination, in which the obtained films served as working electrodes. The experimental results show that the film obtained on the Ag seed layer was rather a pure Ag film and not a Pd/Ag film, and the Ag deposition rate on Pd sites was much faster than that on Ag sites.     

The processes involved in the Se electrodeposition and dissolution on Au electrode: the H<Subscript>2</Subscript>Se formation

The processes involved in the Se electrodeposition, mainly the one related to the formation of H₂Se species on Au electrode in perchloric acid solutions, have been investigated through cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM), rotating ring-disc electrode (RRDE), and atomic force microscopy (AFM) techniques. In the experiments performed with the EQCM, with the potential sweep in the negative direction, the responses for the mass variation were divided in three well-defined potential regions: A (from 1.55 to 0.35 V), B (from 0.35 to −0.37 V), and C (from −0.37 to −0.49 V). It was verified that the following processes can occur, respectively: the species (AuO)₂H₂SeO₃ was desorbed during the AuO reduction, the reduction of Se(IV) to Se(0), and the formation of H₂Se. When the potential was swept in the positive direction, the responses for the mass variation were divided in four well-defined potential regions: D (from −0.49 to 0.66 V), E (from 0.66 to 0.99 V), F (from 0.99 to 1.26 V), and G (from 1.26 to 1.55 V), and the described processes in these regions were, respectively: the Se deposition and adsorption of water molecules and/or perchlorate ions, the Se dissolution, the Se incorporating mass in the form of HO–Se, and the Au oxidation (all potentials are referred to the Ag/AgCl electrode). Making use of the RRDE, using the collection technique, the formation of H₂Se species during the Se electrodeposition was investigated. Therefore, it was confirmed that this species is formed on the disc electrode between −0.3 and −0.55 V vs the Ag/AgCl potential range (collecting the oxidized compound onto the ring electrode). AFM images also indicated that the surface topography of the Se-massive deposit on Au is different from the images registered after the formation of H₂Se species, confirming the cathodic stripping of Se.     

Fabrication of TiO2/Ti nanotube electrode and the photoelectrochemical behaviors in NaCl solutions

Titanium oxide nanotube electrodes were successfully prepared by anodic oxidation on pure Ti sheets in 0.5 wt.% NH₄F + 1 wt.% (NH₄)₂SO₄ + 90 wt.% glycerol mixed solutions. Nanotubes with diameter 40–60 nm and length 7.4 μm were observed by field emission scanning electron microscope. The electrochemical and photoelectrochemical characteristics of TiO₂ nanotube electrode were investigated using linear polarization and electrochemical impedance spectroscopy techniques. The open-circuit potential dropped markedly under irradiation and with the increase of Cl⁻ concentrations. A saturated photocurrent of approximately 1.3 mA cm⁻² was observed under 10-W low-mercury lamp irradiation in 0.1 M NaCl solution, which was much higher than film electrode. Meanwhile, the highest photocurrent in NaCl solution implied that the photogenerated holes preferred to combine with Cl⁻. Thus, a significant synergetic effect on active chlorine production was observed in photoelectrocatalytic processes. Furthermore, the generation efficiency for active chlorine was about two times that using TiO₂/Ti film electrode by sol–gel method. Finally, the effects of initial pH and Cl⁻ concentration were also discussed.     

Preparation and characterization of AuPt alloy nanoparticle–multi-walled carbon nanotube–ionic liquid composite film for electrocatalytic oxidation of cysteine

Gold–platinum (AuPt) alloy particles were fabricated directly on multi-walled carbon nanotubes (MWNT)–ionic liquid (i.e., trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide, [P_6,6,6,14][NTf₂]) composite coated glassy carbon electrode (GCE) by electrodeposition method. Scanning electron microscope image showed that they were well-dispersed nanocluster consisting of smaller nanoparticles, and their size was about 70 nm. X-ray diffraction experiment showed that they were single-phase alloy nanomaterial, and the calculated composition was consisting with that obtained by energy dispersive X-ray spectroscopy. The resulting modified electrode (i.e., AuPt–MWNT–[P_6,6,6,14][NTf₂]/GCE) presented high catalytic activity for the electrochemical oxidation of cysteine. The peak potential of cysteine shifted to 0.42 V (versus saturated calomel electrode) in 0.1 M H₂SO₄ and the peak current increased greatly in comparison with that on the corresponding Pt (or Au)–MWNT–[P_6,6,6,14][NTf₂]/GCE. Under the optimized conditions, the oxidation current of cysteine at 0.45 V was linear to its concentration in the range of 5.0 × 10⁻⁷ ∼ 4.0 × 10⁻⁵ M with a sensitivity of 43.8 mA M⁻¹.     

Photoinduced cathodic deposition of CdTe nanoparticles on polycrystalline gold substrate

A combination of photocathodic stripping and precipitation was used to prepare CdTe nanoparticles (size range: 30–60 nm) that were immobilized on a polycrystalline Au substrate. Thus visible light irradiation of a Te modified Au surface generated Te²⁻ species in situ followed by interfacial reaction with added Cd²⁺ ions in 0.1 M Na₂SO₄ electrolyte. The resultant CdTe compound semiconductor deposited as nanosized particles uniformly dispersed on the Au substrate surface. This approach to CdTe nanoparticle deposition was monitored by a combination of electrochemical methods (voltammetry, chronoamperometry) and quartz crystal microgravimetry in the “dark” and under illumination. The synthesized CdTe nanoparticles were characterized by scanning electron microscopy and energy dispersive X-ray analyses and laser Raman spectroscopy.     

Effect of dioctyl sulfide on the kinetics of oxidative dissolution of gold nanoparticles in triton N-42 reverse micelles

The effect of additions of hydrophobic dioctyl sulfide (L) on the kinetics of dissolution of gold nanoparticles in the interaction with a dispersed aqueous hydrochloric solution of H₂O₂ in Triton N-42 reverse micelles (decane was the dispersion medium) was studied spectrophotometrically. The process consists of a two-stage oxidation Au⁰ → AuCl₂⁻ → AuCl₄⁻ at the surface of gold particles; the first stage occurs in two ways: a spontaneous reaction and an autocatalytic reaction involving AuCl₄⁻ ions. With small additions of L (c _L < c _Au), only spontaneous oxidation of Au(0) to Au(I) takes place because Au(I) is completely bound in an inert complex AuLCl. When unbound L is exhausted, the newly formed AuLCl is accumulated in micellar shells, changes the properties of the medium inside the micelles, and affects the rate constant of the autocatalytic reaction, which increases with increasing c _L. At high concentrations of L, the coagulation of particles occurs instead of their dissolution, because of the deterioration of the protective properties of micellar shells as a result of the ingression and accumulation of dioctyl sulfide molecules on account of selective adsorption on gold particles. The rate constants of all stages of dissolution and coagulation are determined.