Electrochemical degradation of Reactive Red 120 using DSA and BDD anodes

Electrochemical oxidation of an azo dye (Reactive Red 120) was studied in acidic media (1 M HClO₄) using DSA type (Ti/IrO₂–RuO₂) and boron doped diamond (BDD) anodes. Ti/IrO₂–RuO₂ exhibited low oxidation power with high selectivity to organic intermediates and low TOC removal (10% at 25 °C and 40% at 80 °C). On the other hand BDD was found to be suitable for total mineralization of the organic loading to CO₂. In both cases, the decoloration of the solution was almost 100% achieved very quickly with BDD (2 Ah L⁻¹) but only after long treatment with Ti/IrO₂–RuO₂ (25 Ah L⁻¹). The instantaneous current efficiency (ICE) was up to 0.13 in the case of Ti/IrO₂–RuO₂ and up to 0.45 in the case of BDD.     

Preparation and evaluation of RuO2–IrO2, IrO2–Pt and IrO2–Ta2O5 catalysts for the oxygen evolution reaction in an SPE electrolyzer

IrO₂–RuO₂, IrO₂–Pt and IrO₂–Ta₂O₅ electrocatalysts were synthesized and characterized for the oxygen evolution in a Solid Polymer Electrolyte (SPE) electrolyzer. These mixtures were characterized by XRD and SEM. The anode catalyst powders were sprayed onto Nafion 117 membrane (catalyst coated membrane, CCM), using Pt catalyst at the cathode. The CCM procedure was extended to different in-house prepared catalyst formulations to evaluate if such a method could be applied to electrolyzers containing durable titanium backings. The catalyst loading at the anode was about 6 mg cm⁻², whereas 1 mg cm⁻² Pt was used at the cathode. The electrochemical activity for water electrolysis was investigated in a single cell SPE electrolyzer at 80 °C. It was found that the terminal voltage obtained with Ir–Ta oxide was slightly lower than that obtained with IrO₂–Pt and IrO₂–RuO₂ at low current density (lower than 0.15 A cm⁻²). At higher current density, the IrO₂–Pt and IrO₂–RuO₂ catalysts performed better than Ir–Ta oxide.     

Structural analyses of RuO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti and IrO<Subscript>2</Subscript>–RuO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti anodes used in industrial chlor-alkali membrane processes

The morphology and composition of RuO₂–TiO₂/Ti and IrO₂–RuO₂–TiO₂/Ti anodes, which have been used for the production of chlorine for more than 10 years, were analyzed by various methods; such as high-resolution scanning electron microscopy, high-resolution Auger electron spectroscopy, electron probe X-ray emission microanalysis and X-ray diffraction analysis. Drastic changes in the surface morphology, including partial exfoliation of a small amount of the oxide layer and a reduction in the content of ruthenium species through dissolution, were observed for the RuO₂–TiO₂/Ti anode. For the IrO₂–RuO₂–TiO₂/Ti anode, on the other hand, there were moderate changes in the surface morphology and moderate dissolution of iridium and ruthenium species.     

Electrochemical oxidation of an acid dye by active chlorine generated using Ti/Sn<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Ir<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> electrodes

The generation of active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L⁻¹) and a low current density (5 mA cm⁻²) it was possible to produce up to 60 mg L⁻¹ of active chlorine on a Ti/Sn_0.99Ir_0.01O₂ anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm⁻² and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 × 10⁻⁴ mol L⁻¹. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.     

Effect of IrO2 loading on RuO2–IrO2–TiO2 anodes: A study of microstructure and working life for the chlorine evolution reaction

RuO₂–IrO₂–TiO₂/Ti anodes are widely used in chlor-alkali and chlorate industry. The working life is of particular importance for anodes. The relationship between the content of IrO₂ and working life was investigated. The microstructure of the anode with 0.5 mg/cm² IrO₂ is much more homogeneous than those with lower IrO₂ contents. Both the size of particles containing RuO₂ and IrO₂ and the content of rutile TiO₂ phase in anodes decrease with increased IrO₂ content. The working life of anode with 0.5 mg/cm² IrO₂ is almost double that of the anode with 0.3 mg/cm² IrO₂.     

In situ active chlorine generation for the treatment of dye-containing effluents

This study examined the possibility to remove colour causing-compounds from synthetic effluent by indirect electrochemical oxidation using iridium oxide anode electrodes. Using a high concentration of chloride ions (17.1 mM) and various current densities, it was possible to produce high concentration of active chlorine with a specific production rate of 2.8 mg min⁻¹ A⁻¹. The best performance for acid methyl violet 2B dye (MV2B) decomposition was obtained using Ti/IrO₂ anodes operated at a current density of 15 mA cm⁻² during 40 min of treatment in the presence of 3.42 mM of chloride ions. Under these conditions, more than 99% of MV2B was removed (with a reaction rate apparent constant of 0.20 min⁻¹), whereas COD and TOC removal were 51% and 75%, respectively. The electrolytic cell was then used for the degradation of three other synthetic dye solutions: Eosin yellowish (EOY), Trypan Blue (TRB), Acridine Orange (ACO). TRB was the most difficult dye to remove from solution with a value reaction rate constant of 0.12 min⁻¹, compared to 0.19 min⁻¹ and 0.24 min⁻¹ recorded for ACO and EOY dyes, respectively. More than 99% of these dyes were removed by electrochemical oxidation.     

Removal of geosmin (trans-1,10-dimethyl-trans-9-decalol) from aqueous solution using an indirect electrochemical method

Geosmin was effectively removed using an electrochemical method at the Ti/RuO₂-Pt anode in the presence of NaCl as a reactant. At a current density of 40 mA cm⁻², the geosmin concentration decreased from 600 ng L⁻¹ to 6 ng L⁻¹ in 60 min in the presence of 3.0 g L⁻¹ NaCl. HOCl formed during electrolysis would likely play an important role in the geosmin oxidation. The electrochemical method exhibited good performance for geosmin removal under various conditions. The geosmin removal rate increased with increasing current density, while the geosmin removal rates were similar at different initial pH values. The Ti/RuO₂-Pt anode also performed well for electrochemical degradation of geosmin at both low and high concentrations. According to the present experimental results, the electrochemical method should be a promising alternative for the efficient and rapid removal of musty odor compounds in a water treatment process.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Enhanced electrochemical performance of FeS<Subscript>2</Subscript> synthesized by hydrothermal method for lithium ion batteries

Iron disulfide (FeS₂) powders were successfully synthesized by hydrothermal method. Cetyltrimethylammonium bromide (CTAB) had a great influence on the morphology, particle size, and electrochemical performance of the FeS₂ powders. The as-synthesized FeS₂ particles with CTAB had diameters of 2–4 μm and showed a sphere-like structure with sawtooth, while the counterpart prepared without CTAB exhibited irregular morphology with diameters in the range of 0.1–0.4 μm. As anode materials for Li-ion batteries, their electrochemical performances were investigated by galvanostatic charge–discharge test and electrochemical impedance spectrum. The FeS₂ powder synthesized with CTAB can sustain 459 and 413 mAh g⁻¹ at 89 and 445 mA g⁻¹ after 35 cycles, respectively, much higher than those prepared without CTAB (411 and 316 mAh g⁻¹). The enhanced rate capability and cycling stability were attributed to the less-hindered surface layer and better electrical contact from the sawtooth-like surface and micro-sized sphere morphology, which led to enhanced process kinetics.     

Effects of the geometry and operating temperature on the stability of Ti/IrO<Subscript>2</Subscript>–SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>5</Subscript> electrodes for O<Subscript>2</Subscript> evolution

Ternary IrO₂–Sb₂O₅–SnO₂ anode has shown its superiorities over IrO₂ and many other electrocatalysts for O₂ evolution, in terms of electrochemical stability, activity and cost. The performance of IrO₂–Sb₂O₅–SnO₂ anodes is affected by its electrochemical properties and operating conditions. In this paper, the electrochemical stability and activity of the Ti/IrO₂–Sb₂O₅–SnO₂ anodes prepared with three different geometries were investigated under different operating conditions. It was found that anodes with large mean curvature have high electrochemical stability. Although increasing temperature results in a decrease in the stability of Ti/IrO₂–Sb₂O₅–SnO₂, the anode with a mean curvature of 200 m⁻¹ still shows acceptable service life even at 70 °C. This tolerance of high temperature was attributed to the thermal expansion difference between the substrate and the coating layer, the redox window for Ir(V)/Ir(IV) conversion, and the redox reversibility of Sb and Sn species in the coating layer.     

Determination of hydrogenation ability and exchange current of H<Subscript>2</Subscript>O/H<Subscript>2</Subscript> system on hydrogen-absorbing metal alloys

A detailed analysis of potential versus time measurements at galvanostatic charge/discharge conditions (external current change from −1 to +1 mA cm⁻²) for two La–Ni alloys in Ar-saturated 0.1 M KOH solution is presented. It is shown that passivation of the electrodes does not affect the potential jump as a result of current switching over. The value of potential jump allows to calculate the exchange current density for H₂O/H₂ system on the tested material. Anodic potential of the hydrogenated electrode (at i _a = const) linearly increases with logarithm of time which allows to evaluate precisely time necessary for oxidation of hydrogen absorbed during cathodic charging. The method described enables to determine effectiveness of hydrogen absorption by materials applied for negative electrodes of NiMH batteries.     

The Effects of Co-Sensitization and Electronic Structure of Nanocrystalline N/TiO<Subscript>2</Subscript> Anode on the Performance of Dye-Sensitized Solar Cells

N/TiO₂ nanocrystalline film anodes were obtained by doping nonmetallic element N which could change the LUMO of anode. This paper also studied the match between the LUMO energy lever of N/TiO₂ anode and the dye, which led to the easy injection of electron from the excited state of dye molecule to the conduction band of semiconductor, and thus improved the photoelectric conversion efficiency and reduced the impedance of solar cells. The solar cell based on N/TiO₂ anode film co-sensitized by P3HT (poly(3-hexylthiophene))/N719(RuL2(NCS)2:2TBA (L = 2,2′-bipyridyl-4,4′-dicarboxylic acid)), the absorption region of which covered the entire visible region in solar cells, showed a short-circuit current density of 6.88 mA cm⁻², an open-circuit voltage of 0.616 V, and a photoelectric conversion efficiency of 2.34%.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

Preparation and electrochemical performance of SiCN–CNTs composite anode material for lithium ion batteries

The composite of silicon carbonitride (SiCN) and carbon nanotubes (CNTs) was synthesized by sintering the mixture of polysilylethylenediamine-derived amorphous SiCN and multi-walled CNTs at a temperature of 1,000 °C for 1 h in argon. The as-prepared SiCN–CNTs material, which was used as anode active substance in a lithium ion battery, showed excellent electrochemical performance. Charge–discharge tests showed the SiCN–CNTs anode provided a high initial specific discharge capacity of 1176.6 mA h g⁻¹ and a steady specific discharge capacity of 450–400 mA h g⁻¹ after 30 charge–discharge cycles at 0.2 mA cm⁻². Both of the abovementioned values are higher than that of pure polymer-derived SiCN, CNTs, and commercial graphite at the same charge–discharge condition. It was deduced that the CNTs in the composite not only improved the electronic conductivity and offered channels and sites for the immigrating and intercalating of Li⁺ but also stabilized the structure of the composite.     

Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Studies of some operating parameters and cyclic voltammetry for a direct ethanol fuel cell

A direct ethanol fuel cell (DEFC) of 5 cm² membrane-electrode area was studied systematically by varying the catalyst loading, ethanol concentration, temperature and different Pt based electro-catalysts (Pt–Ru/C, Pt-black High Surface Area (HSA) and Pt/C). A combination of 2 M ethanol at the anode, pure oxygen at the cathode, 1 mg cm⁻² of Pt–Ru/C (40%:20%) as the anode and 1 mg cm⁻² of Pt-black as the cathode gave a maximum open circuit voltage (OCV) of 0.815 V, a short circuit current density of 27.90 mA cm⁻² and a power density of 10.3 mW cm⁻². The optimum temperatures of the anode and cathode were determined as 90 °C and 60 °C, respectively. The power density increased with increase in ethanol concentration and catalyst loading at the anode and cathode. However, the power density decreased slightly beyond 2 M ethanol concentration and 1 mg cm⁻² catalyst loading at the anode and cathode. These results were validated using cyclic voltammetry at single electrodes under similar conditions to those of the DEFC.     

Treatment of wastewater from synthetic textile industry by electrocoagulation–electrooxidation

Treatment of wastewater from a textile industry that produces synthetic polyester cloths was studied employing electrochemical techniques. The sample was initially subjected to electrocoagulation to remove suspended solids. Mild steel and aluminum electrodes were tried as anodes; and aluminum was found to be effective for the removal of suspended solids. Using aluminum as anode, the chemical oxygen demand (COD) concentration of the effluent which was initially at the level of 1316 mg L⁻¹ could be reduced to 429 mg L⁻¹ by electrocoagulation. After electrocoagulation, the effluent was further subjected to electrooxidation using graphite and RuO₂/IrO₂/TaO₂ coated titanium as anodes. During the electrooxidation tests, both COD and chloride ion were simultaneously estimated; and the effect of Cl⁻ ion is discussed. The measurements have revealed the depletion of Cl⁻ ion concentration implying the generation of free chlorine during electrooxidation. The depletion of Cl⁻ ion concentration and the COD removal were observed to be comparatively high in the presence of graphite electrode. The effects of electrode materials and current density on COD removal are discussed. The instantaneous current efficiency (ICE), mass transfer coefficient and energy consumption were estimated.     

Chemical and electrochemical characterization of TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> atomic layer depositions on AZ-31 magnesium alloy

In this study, innovative TiO₂/Al₂O₃ mono/multilayers were applied by atomic layer depositions (ALD) on ASTM-AZ-31 magnesium/aluminum alloy to enhance its well-known scarce corrosion resistance. Four different configurations of ALD layers were tested: single TiO₂ layer, single Al₂O₃ layer, Al₂O₃/TiO₂ bilayer and Al₂O₃/TiO₂/Al₂O₃/TiO₂ multilayer deposited using Al[(CH₃)]₃ (trimethylaluminum, TMA), and TiCl₄ and H₂O precursors. All depositions were performed at 120°C to obtain an amorphous-like structure of both oxide layers. The four coatings were then investigated using different techniques, such as scanning electron microscope (SEM), stylus profilometer, glow discharge optical emission spectrometry (GDOES) and polarization curves in 0.05-M NaCl solution. The thickness of all the coatings was around 100 nm. The layers compositions were successfully investigated by the GDOES technique, although obtained data seem to be affected by substrate roughness and differences in sputtering rates between ceramic oxides and metallic magnesium alloy. Corrosion resistance showed to be strongly enhanced by the nanometric coatings, giving lower corrosion current densities in 0.05-M NaCl media with respect to the uncoated substrate (from 10⁻⁴ to 10⁻⁶ A/cm² for the single layers and from 10⁻⁴ to 10⁻⁸ A/cm² for the bi- and multilayers). All polarization curves on coated samples also showed a passive region, wider for the bi-layer (from −0.58 to −0.43 V with respect to Ag/AgCl) and multilayer (from −0.53 to −0.38 V with respect to Ag/AgCl) structures.     

Investigation of N<Subscript>2</Subscript>-fixation on polyaniline electrodes in methanol by electrochemical impedance spectroscopy

The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the N₂-fixation in methanol + LiClO₄ electrolyte with 0.03 mol L⁻¹ H₂SO₄ for the first time. The optimum film thickness was found to be 1.5 μm, N₂-pressure 50 bar and an optimum electrolysis potential of −0.12 V (NHE). The diffusion coefficients for N₂ into the polymer film was found to be (5 ± 2)×10⁻⁹ cm² s⁻¹.     

Anodic oxidation of organic pollutants on a Ti/SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>4</Subscript> anode

A Ti/SnO₂–Sb₂O₄ electrode was prepared by alternate Sn and Sb electrodepositions using the thermo-electrochemical method. The chemical, electrochemical, and structural characterization of the electrode was performed and it was tested in the anodic oxidation of several pollutants, phenol, ibuprofen, acid orange 7 (AO7), and diclofenac, all in aqueous 0.035 M Na₂SO₄ solutions at current densities of 10 and 20 mA cm⁻². After the 24 h assay, removal of chemical oxygen demand, total organic carbon (TOC) and absorbance were very high, especially at the higher current density. TOC removals presented the lowest value. However, after 24 h at 20 mA cm⁻², TOC removals were: phenol—94%; ibuprofen—83%; AO7—88%; and diclofenac—73%. Combustion efficiency and instantaneous and mineralization current efficiencies were also determined.