The impedance of fast charge transfer reactions on boron doped diamond electrodes

Reversible charge transfer on boron doped diamond (BDD) electrodes was studied using cyclic voltammetry and electrochemical impedance spectroscopy. Polycrystalline diamond films of 5 μm thickness with 200 and 3000 ppm boron content were prepared by chemical vapour deposition on niobium substrate. The samples were mounted in a Teflon holder and used as rotating disk electrodes (RDE) with rotation frequencies between 0 and 4000 rpm. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na₂SO₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆] and 0.1 M KCl + 5 mM [Ru(NH₃)₆]Cl₂/[Ru(NH₃)₆]Cl₃. The electrochemical redox behaviour of the BDD electrodes was found to differ significantly from that of an active Pt electrode. The deviations are indicated by a large peak potential difference and a shift of the peak potentials in cyclic voltammograms with increasing sweep rate. At rotating electrodes lower limiting current densities are found and the impedance diagrams exhibit an additional capacitive impedance element at high frequencies. The results are described quantitatively by an impedance model which is based on partial blocking of the diamond surface.     

Influence of anolyte and catholyte composition on TPHs removal from low permeability soil by electrokinetic reclamation

Removal of TPHs from polluted soil by electrokientic reclamation was done by using different electrolytes (anolyte and catholyte). The initial concentration of TPHs in soil was 23,000 ppm and removal efficiencies reached almost 90% for a combination of 0.04 M NaOH and 0.1 M Na₂SO₄ in the anode and cathode chambers, respectively. Electroosmotic flow and TPHs desorption were measured under galvanostatic conditions (1.95 mA cm⁻² and electric field <10 V cm⁻¹). The study is supported on the electrokinetic transport model for low permeability soils. Electrolytes (anolyte and catholyte) were maintained at constant ionic composition to keep constant boundary conditions, thus launch a pseudostationary state for fluid and charge transport throughout the soil. It was also observed that electrolyte concentration favored TPHs desorption as well as their transport throughout the soil by electroosmotic flow from anode to cathode. Both, electrolytes concentration and wetting solution helped to maintain a constant pH profile during electroreclamation, thus a sustained fluid flow from anode to cathode.     

Testing pulsed electric fields in electroremediation of copper mine tailings

Mining processes, prior to pyrometallurgical copper production, generate large amounts of solid waste, which are and have been deposited in mine tailings impoundments. This work is based on three electrodialytic (EDR) and four electrokinetic (EKR) remediation experiments on fresh and aged copper mine tailings using pulsed electric fields. The EDR results are compared to conventional remediation with direct current (dc) electric field. Applying pulsed electric fields in EDR, it was found that the remediation time decreased compared to dc EDR. In the anode side of the cell, 72 h of remediation at 20 V with a frequency ≥28 cycles/day at a fixed time ratio (t_ON/t_OFF) of 20, in terms of copper removal would correspond to around 270 h of dc remediation time. With both EDR and EKR of 120 h, at 14 cycles/day, the copper removal is practically uniform in the whole cell. Increasing the frequency to ≥28 cycles/day, the copper removal in the anode side is improved, and in the cathode side an accumulation is observed. With an EKR of 240 h, a larger copper accumulation in the cathode side was observed due to precipitation of copper hydroxide. In EDR with a pulsed electric field, the transport across the cation exchange membrane becomes the rate determining step. This can be seen from: (a) accumulation in the cathode side when increasing the frequency and (b) similar total copper removal for the three frequencies studied. In EKR, free alkali diffusion into the cell occurred. This generated copper precipitation in the cathode side, and the effect of the pulsed electric field on total copper removal was reduced.     

Colour removal of three reactive dyes by UV light exposure after electrochemical treatment

This study applies UV light irradiation after a low current density electrochemical treatment to degrade reactive dyes to remove wastewater colour. The combination of these two techniques improves the quality of the treated effluent with respect to only an electrochemical treatment. Synthetic dyeing effluents containing a reactive dye (C.I. Reactive Orange 4, C.I. Reactive Black 5 or Procion Navy H-EXL) and Na₂SO₄ were studied. Ti/Pt oxides electrodes and UV irradiation lamp (6 W, 254 nm maximum emission) were used. Kinetic constants of the UV irradiation step were calculated. The influence of chloride ion at 3 and 6 mA/cm² was evaluated. Results showed that, with a very small Cl^? concentration (in the order of the net water content) the combined techniques provided full decolourization. The possible presence of 25 organic halogenated compounds was studied by gas chromatography–mass spectrophotometry (GCMS). Only four of them were detected after the electrochemical treatment at low intensity, mainly chloroform. Its concentration was found to be highly dependent of the Cl^? concentration, being much lower when reducing the amount of chloride ion. In all cases, the chloroform concentration was dramatically reduced by further UV irradiation which destroyed it up to a 75%.     

Electrosyntheses of poly(neutral red), a polyaniline derivative

The electrochemical oxidation of neutral red in 0.5 mol dm⁻³ H₂SO₄ solution was carried out by using repeated potential cycling between −0.20 and 1.20 V (versus SCE). The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 4.0. The result from the X-ray photoelectron spectroscopy (XPS) experiment shows that the anions can be doped into the polymer film during the electropolymerization reaction of neutral red. The scanning electron microscopy (SEM) micrograph shows the surface of poly(neutral red) film deposited on the platinum foil is covered with a micro-structured network of mass interwoven fibers with a diameter of 2-4 μm. A straight fiber of the unsystematic micro-fibers is longer than 0.4 mm. The UV-vis spectrum and infrared spectrum (IR) of the polymer are different from those of the monomer.     

Nanosized α-LiFeO2 as electrochemical supercapacitor electrode in neutral sulfate electrolytes

In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of α-LiFeO₂ in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li₂SO₄ solution and voltage range studied was between 0 and −0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of ≈50 F g⁻¹ is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na₂SO₄, K₂SO₄, Cs₂SO₄) were investigated as electrolytes but only Li₂SO₄ leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO₂ as negative and positive electrodes, respectively, delivered 0.3 F cm⁻² (10 F g⁻¹). Although these values are lower than reported for other aqueous hybrid cell, α-LiFeO₂/MnO₂ asymmetric capacitor is interesting from both, an economic and an environmental point of view.     

Structural and electrochemical properties of a K2FeO4 cathode for rechargeable Li ion batteries

Ferrate is considered to be a potential cathode material for high-energy batteries, due to its high capacity based on three-electron transfer in electrochemical reactions. In this work, high-purity potassium ferrate (K₂FeO₄) was synthesized by a direct hypochlorite oxidation method. X-ray diffraction (XRD) and a charge-coupled device (CCD) were used to characterize the structure of the K₂FeO₄ as well as the channels for intercalation-deintercalation of Li ions. The one-dimension channel was observed in the direction of the a and b axes in the unit cell, with a radius 0.93 Å, which is beneficial for Li ion (radius = 0.76 Å) intercalation and deintercalation in K₂FeO₄. The experimental super-iron Li ion battery was assembled with 1 M LiPF₆ organic electrolyte (PC:EC:DMC = 1:3:6, v/v), a K₂FeO₄ cathode, and a metal lithium anode. The electrochemical performance of the K₂FeO₄ cathode was evaluated by a galvanostatic method and cyclic voltammetry (CV) in the potential range of 4.3-0.5 V at room temperature. It was demonstrated that one Li ion intercalates into the lattice of the K₂FeO₄ cathode along the channels of the a and b axes of the K₂FeO₄ unit cell, followed by a two-Li ion intercalation of isotropy in the initial discharge process. Amorphization of the K₂FeO₄ cathode is the main cause of its electrochemical performance decay.     

Electrochemical behaviour of glassy carbon electrodes modified with aryl groups

The electrochemical modification of the glassy carbon (GC) electrode surface with biphenyl, 1-naphthyl, 2-naphthyl, 4-bromophenyl, 4-decylphenyl and 4-nitrophenyl groups was performed by the diazonium reduction method. The blocking behaviour of aryl films grafted by three different procedures was compared. Oxygen reduction was studied on these modified GC electrodes using the rotating disk electrode (RDE) method. The highest blocking efficiency for O₂ reduction was observed for 4-bromophenyl groups. The barrier properties of aryl-modified GC surfaces were also characterised using Fe(CN)₆³⁻ and dopamine redox probes. Electrochemical measurements were carried out in 0.1 M K₂SO₄ containing 1 mM K₃Fe(CN)₆ and in 0.1 M H₂SO₄ containing 1 mM dopamine using cyclic voltammetry (CV). The blocking action varied significantly depending on the surface modifier used and the solution based redox species studied.     

Electrosynthesis of poly(neutral red) incorporated with ferrocenesulfonic acid

The electrochemical oxidation of neutral red in 0.5 mol dm⁻³ sulfuric acid and 0.2 mol dm⁻³ ferrocenesulfonic acid solution was carried out using repeated potential cycling between −0.20 and 1.40 V (versus SCE). The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 7.0. The result from the X-ray photoelectron spectroscopy (XPS) experiment shows that the anions can be doped into the polymer film during the electrochemical polymerization reaction of neutral red. The scanning electron microscopy (SEM) micrograph shows that the surface of the resulting polymer film formed on the platinum foil is covered with a compact surface consisting of micro fibers. The visible spectrum and infrared spectrum (IR) of the polymer are different from those of the corresponding monomer. A possible chemical structure of the resulting polymer was also proposed.     

Influence of ionic speciation on electrocatalytic performance of polyaniline coated platinum electrode: Fe(III)/Fe(II) redox reaction

Porous-polyaniline coated Pt electrode (PANI/Pt) was electro-synthesized potentiodynamically in 0.1 M aniline + 0.5 M H₂SO₄ and morphologically characterized by scanning electron microscopy (SEM). Nature of predominant Fe-species in HCl and H₂SO₄ was checked by UV-vis spectrophotometry. Electrocatalysis of Fe(III)/Fe(II) reaction was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for three different solution compositions viz. (i) FeCl₃/FeCl₂ in 1 M HCl, (ii) FeCl₃/FeCl₂ in 0.5 M H₂SO₄ and (iii) Fe₂(SO₄)₃/FeSO₄ in 0.5 M H₂SO₄. For different thicknesses of PANI, the peak current increased irrespective of the nature of the Fe-species, but the polarity of the charge on the Fe-species showed great influence on reversibility of electrocatalysis by PANI/Pt. The Donnan interaction of the polyaniline modified electrode for the three compositions was investigated with respect to [Fe(CN)₆]³⁻/H₂[Fe(CN)₆]²⁻ which are believed to be the predominant species present in K₃[Fe(CN)₆]/K₄[Fe(CN)₆] solution in 0.5 M H₂SO₄. The electrocatalytic performance of PANI/Pt for Fe(III)/Fe(II) redox reaction was found superior in HCl compared to that in H₂SO₄.     

Electrochemical polymerization of neutral red in the presence of sulfoferrocenecarboxylic acid

Syntheses, properties and applications of polyaniline and its derivatives have been studied extensively. Recent papers have shown that their micro-structures can be prepared using chemical, electrochemical and physical methods. Here, we describe oxidative polymerization of neutral red, an aniline derivative, carried out in aqueous sulfuric acid solution containing sulfoferrocenecarboxylic acid using repeated potential cycling. The polymer film was electrochemically deposited on a platinum anode and had an electrochemical activity in the solution of 0.5 mol dm⁻³ Na₂SO₄ with pH ≤ 7.0. Based on the spectroscopic measurements, a possible chemical structure of the corresponding polymer was proposed. The scanning electron microscopy micrograph proved that the micro-structure of the resulting polymer, which portrayed geological features similar to Earth and Titan, can be prepared using the electrochemical method.     

Improved electrochemical CO removal via potential oscillations in serially connected PEM fuel cells with PtRu anodes

The polarization performance of two PEM fuel cells (with anode PtRu/C catalyst) connected either in parallel or serial, was compared to the performance of a single PEM fuel cell in galvanostatic operation using CO-free H₂ or 200 ppm CO-containing H₂ stream as anode feed at ambient temperature. Spontaneous potential oscillations were observed experimentally for the coupled configuration with two cells connected in serial or parallel using CO-containing H₂ feed at various current densities applied. The potential oscillations are ascribed by the dynamic CO adsorption and subsequent electrochemical CO oxidation on the anode. The measured anode outlet CO concentration was found to decrease with the order: single cell > parallel cells > serial cells at various current densities and anodic flow rates. The low anode outlet CO concentration (<10 ppm) at high current densities applied showed that CO in the anode feed was removed efficiently by the electrochemical CO oxidation occurring on the PtRu anode. The anode outlet CO concentration decreased as follows: a single cell > the parallel cells > the serial cells at broad range of current densities and anodic flow rates. The highest CO conversion and the highest average power output at equal hydrogen recovery degree were obtained with serially coupled fuel cells.     

Anodically synthesized titania films for lithium batteries: Effect of titanium substrate and surface treatment

A number of titania films have been produced through anodising high purity titanium from different suppliers in either the as-received state or following polishing and etching. Anodising was carried out galvanostatically for a period of 10 min in 0.2 M H₂SO₄. The performance of the films was then evaluated as potential anode materials for lithium batteries. Raman spectroscopy showed these films had spectra characteristic of anatase with the presence of some rutile whilst the spectra of the lithiated state was characteristic of the orthorhombic phase of Li_xTiO₂.The surface condition in particular was found to have an effect on the electrochemical performance and properties of the films most notably on capacity fade. Whilst the electrodes produced from as-received titanium demonstrated stable cycle capacities after the initial few cycles, those on polished and etched substrates faded over 50 cycles. The best performing films offered a capacity of at least ∼48 μAh cm⁻² over the 50 cycles. All the electrodes examined however did show signs of the film having being damaged as a result of electrochemical cycling. With the wide range of anodising parameters that can be altered there is considerable scope for optimising the electrochemical performance of films produced through such a technique.     

Electrocatalytic activity of electrodeposited composite films of polypyrrole and CoFe2O4 nanoparticles towards oxygen reduction reaction

Electrochemical behaviour of sandwich-type composite electrodes of polypyrrole (PPy) and CoFe₂O₄ nanoparticles (Ox) were investigated in an aqueous solution of 0.5 M K₂SO₄ and 5mM KOH at 25 °C using electrochemical impedance (EI), cyclic voltammetry (CV) and Tafel polarization techniques. EI and CV studies indicated that the incorporation of oxide nanoparticles influenced the charge transfer and transport behaviours of the polymer matrix greatly. The bulk electrical resistances of pure polymer (4.5 ± 1.7 Ω) as well as composite (2.7 ± 0.8 Ω) electrodes were practically constant in the potential region, +0.1 to −0.7 V. The latter electrode showed a good electrocatalytic activity towards the oxygen reduction reaction (ORR).     

The effects of catalysts on the carbothermic reduction of zinc sulfide in the presence of calcium oxide

The effects of the type and the amount of various catalysts on the rate of the carbothermic reduction of zinc sulfide in the presence of calcium oxide were studied using thermogravimetric analysis system (TGA). Experimental results revealed that the order of the effects of the catalysts is Li₂CO₃ ≈ Na₂CO₃ ≈ Na₂SO₄ > Li₂SO₄ > K₂CO₃ > K₂SO₄. It was also observed that with more Li₂CO₃ the reaction is faster, when the amount of Li₂CO₃ was less than 2.0 wt.%.     

Effect of clay mineralogy on the feasibility of electrokinetic soil decontamination technology

To evaluate the effect of clay mineralogy on the feasibility of electrokinetic soil remediation technology, we contaminated six soils with Cu(II), Zn(II) and Pb(II) and performed electroremediation for 570 h. Cation exchange resin saturated with H⁺ was placed between soil and cathode to prevent soil alkalinization and trap the migrated heavy metal cations. After the treatment, the heavy metal cations were sequentially extracted with water, 1 M MgCl₂ and hot 6 M HCl. In soils dominated by crystalline clay minerals, Cu(II) and Zn(II) significantly migrated from anode end and accumulated at the cathode end forming sparingly soluble hydroxides. Removal rates of Cu(II) and Zn(II) were highest in a soil dominated with kaolinite and crystalline hematite. In humic–allophanic and allophanic soils, the high pH-buffering capacity of allophane kept the soil pH above 5, even at the anode end, and Cu(II) and Zn(II) did not migrate significantly. In all soils, the migration of Pb(II) was infinitesimal due to the formation of insoluble PbSO₄ and very strong surface complexation at the mineral surfaces. These results show that the reactivity of component clay minerals to H⁺ and heavy metal cations has a crucial effect on the efficiency of the electrokinetic remediation technology and it is not effective for remediation of allophanic soils. The results also indicate that allophanic soils may be useful as a barrier material in landfill sites.     

Electrochemical potential noise of 321 stainless steel stressed under constant strain rate testing conditions

An investigation was carried out on the features of potential electrochemical potential noise of stressed AISI321 stainless steel in solution 0.5 mol/L Na₂SO₄ + 5 × 10⁻³ mol/L H₂SO₄ under constant-strain-rate-testing (CSRT) conditions. The results showed that the strained steel exhibited a white noise feature at low frequencies and the amplitude of potential fluctuation depended on elongation of the steel. Power spectral density (PSD) of the noise increased with increasing strain level. The noise level in the elastic region of the steel was relatively low, which increased with elongation. After the steel yielded, the electrochemical noise level became higher but it increased less significantly with increasing strain. In the fracture region, the potential noise reached the maximum level. In addition to the dependence of electrochemical noise on strain level, it was also found that the electrochemical noise level increased with increasing strain rate. To interpret the generation mechanism of electrochemical noise, a simple model was proposed based on an assumption that strain results in breakdown and repairing of the passive film on the steel. With this model, the dependence of electrochemical potential noise and its power spectral density on strain level and strain rate can be successfully explained.     

Electrochemical performance of gel-cast NiO-SDC composite anodes in low-temperature SOFCs

NiO-Ce_0.8Sm_0.2O_1.9 (SDC) composites were synthesized using gel-casting technique. The electrochemical performance of the gel-cast (GC) Ni-SDC cermet as anode was investigated contrast with that fabricated from traditional mechanical mixing (MM) technique using fuel cells with about 35 μm-thick SDC electrolyte and Sm_0.5Sr_0.5CoO₃-SDC cathode. Maximum power density of the cell with GC anode achieved 491 mW cm⁻² at 600 °C, over 100 mW cm⁻² larger than that with MM anode, inferring high catalytic activity of the GC anode. Impedance measurements on the fuel cell at open circuit showed that the anodic interfacial polarization resistance of the GC anode was 0.1 Ω cm² lower than that of the MM anode. Long-term stability of the cell with GC anode in hydrogen was also performed, which showed that it can stabilize at least 7 days.     

Photocatalytic Degradation of Two Commercial Reactive Dyes in Aqueous Phase Using Nanophotocatalysts

This study involves the photocatalytic degradation of Reactive Black 5 (RB5) and Reactive Orange 4 (RO4) dyes, employing heterogeneous photocatalytic process. Photocatalytic activity of different semiconductors such as titanium dioxide (TiO₂) and zinc oxide (ZnO) has been investigated. An attempt has been made to study the effect of process parameters through amount of catalyst, concentration of dye, and pH on photocatalytic degradation of RB5 and RO4. The experiments were carried out by varying pH (3–11), amount of catalyst (0.25–1.5 g/L), and initial concentration of dye (10–100 mg/L). The optimum catalyst dose was found to be 1.25 and 1 g/L for RB5 and RO4, respectively. In the case of RB5, maximum rate of decolorization was observed in acidic medium at pH 4, whereas the decolorization of RO4 reached maximum in basic region at pH 11. The performance of photocatalytic system employing ZnO/UV light was observed to be better than TiO₂/UV system. The complete decolorization of RB5 was observed after 7 min with ZnO, whereas with TiO₂, only 75% dye degraded in 7 min. In the case of RO4, 92 and 62% decolorization was noticed in the same duration.     

Effects of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels in acidic chloride solutions

The role of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels was investigated in 0.5 M H₂SO₄, 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions using potentiodynamic polarization, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. The passive film stability was enhanced in 0.5 M H₂SO₄ and the pitting resistance was improved in 3.5% NaCl solution by more nitrogen addition. The influence of nitrogen extended the whole anodic polarization region in 0.5 M H₂SO₄ + 0.5 M NaCl solution, as demonstrated by the enhanced dissolution resistance, promoted adsorption and passivation process, improved film protection and pitting resistance with increasing nitrogen content. Possible mechanisms relating to the role of nitrogen in different potential regions were discussed.