Electrochemical supercapacitor application of pervoskite thin films

We have explored electrochemically deposited pervoskite nanocrystalline porous bismuth iron oxide (BiFeO₃) thin film electrode from alkaline bath for electrochemical supercapacitors. The pervoskite BiFeO₃ nanocrystalline thin film electrode showed comparable specific capacitance of 81 F g⁻¹ and electrochemical supercapacitive performance and stability in an aqueous NaOH electrolyte to that of commonly used ruthenium based pervoskites.     

Electrochemical deposition of uranium dioxide coatings on alloy 600: effect of annealing on Ni and Cu interlayer mixing

3.5–4.75 mg cm⁻² thick UO₂ coatings were electrodeposited using alkaline uranyl nitrate-ammonium oxalate bath on alloy 600 onto which nickel and copper interlayers were previously electrochemically formed. Micro laser Raman spectroscopy of annealed coating confirmed the formation of UO₂ by showing a peak at 447 cm⁻¹. Scanning electron microscopy showed uniform morphology with an average grain size of 1 µm. Glow discharge optical emission spectroscopy revealed no significant diffusion of nickel and copper into UO₂ due to annealing. Rutherford backscattering spectroscopy showed increased thickness of annealed coating. Scratch adhesion test indicated improved cohesive and adhesive strength of coating after annealing.

     

Preparation and electrochemical properties of Co3O4-coated layered manganese oxide by a novel coating method

Potassium type birnessite (K-bir) was synthesized by O₂ oxidizing Mn²⁺ in aqueous solution of KOH. Co₃O₄-coated K-bir (Co-K-bir) was prepared by employing a novel coating method, in which the remaining OH⁻ ions on the particle surface of the as-precipitated K-bir reacted with Co²⁺ ions in aqueous solution, forming CoOOH coverage; the coating layer of CoOOH was subsequently annealed at 300 °C to transform into Co₃O₄. All the K-bir and Co-K-birs were investigated by scanning electron microscopy, transmission electron microscopy, inductive coupled plasma–atomic emission spectroscopy, Brunauer–Emmett–Teller specific area, and laser particle size analyzing techniques. Their electrochemical properties were also studied by discharging–charging at constant current. The results show that the covering layers of Co₃O₄ are incompact, and their average thickness are about 0.65–0.78 μm. Compared to the as-prepared and the annealed K-bir, the Co₃O₄-coated samples have higher initial discharge capacities and show distinctly improved cycleability performance.     

Photocatalytic efficiency of nanocrystalline zeolite TS-1 for the degradation of methyl orange

The photocatalytic properties of nanocrystalline TS-1 were confirmed via the degradation of an aqueous solution of the model compound methyl orange (MO). The light intensity and quantum yield were measured by ferrioxalate actinometry and the values are 1.7 × 10⁻⁵ einstein l⁻¹ s⁻¹ and 0.71, respectively. The experimental parameters such as catalyst loading, pH and initial concentration of MO were optimized at 1.5 g/L, 10 and 300 μM, in order. The results showed that the dye molecules are completely degraded to CO₂, H₂O and simple inorganic ions.     

Chitosan–magnetite nanocomposites (CMNs) as magnetic carrier particles for removal of Fe(III) from aqueous solutions

This research focuses on removal of Fe(III) from aqueous solution using chitosan–magnetite nanocomposites as potential sorbent. The presence of nanosized magnetic particles within the nanocomposites was confirmed by TEM and SAED analysis. The particles with diameter 508 μm and 84 μm, follow Frendlich sorption isotherm at 30 °C, and the Frendlich constants (K_F, 1/n) have been found to be 5.974 mg g⁻¹, 2.66 and 35.98 mg g⁻¹, 1.385, respectively. Out of various kinetic models, the experimental data for dynamic uptake of Fe(III) is best fitted on ‘pseudo-second order’ kinetic model. The linear nature of plots between log (% sorption) and log (time) is indicative of intra-particle diffusion. For the particles with diameters 508 μm and 84 μm, the value of k_id was found to be 1.78 mg l⁻¹ min^−0.5 and 2.13 mg l⁻¹ min^−0.5. The sorption mean free energy from the Dubinin–Radushkevic isotherm was found to be 7.04 kJ mol⁻¹ indicating chemical nature of sorption. The increase in chitosan content in sorbent particles is found to enhance the Fe(III) uptake. The various thermodynamic parameters have also been evaluated. Finally, the presence of Cu²⁺ ions in the sorbate is found to decrease the uptake of Fe(III).     

Micelle mediated methodology for the determination of free and bound iron in wines by flame atomic absorption spectrometry

A methodology utilizing the cloud point phenomenon for the determination of free and tannin-bound iron in wines is presented. The method employs precipitation of the tannins and other phenolic and insoluble compounds in the micelles of a non-ionic surfactant mixture (TX-100 and TX-45) upon increase of the solution temperature, which are subsequently separated from the initial solution by centrifugation. The surfactant-rich-phase containing the tannins and the insoluble iron fraction is directly aspirated into the nebulizer of a flame atomic absorption spectrometer after its uptake with a methanolic solution of HNO₃. The supernatant is submitted to the same cloud point extraction procedure for the determination of free iron species in the presence of a chelating agent, ammonium pyrrolidine dithiocarbamate (APDC), in order to form water-insoluble complexes with free iron. The complexes are extracted in the micelles and directly analyzed after they are diluted in a methanolic solution as described above. The total content of iron was also determined by conventional methods for comparison, yielding satisfactory results.The calibration graph was rectilinear up to 0.35 mg l⁻¹ Fe, with detection limits of 0.02 mg l⁻¹ with a relative standard deviation of 2.4%. The method was successfully applied to red and white wines.     

PVP-Assisted ZrO2 coating on LiMn2O4 spinel cathode nanoparticles prepared by MnO2 nanowire templates

LiMn₂O₄ spinel nanorods prepared from nanowire MnO₂ templates were capped with polyvinyl pyrrolidone (PVP) and coated with ZrC₂O₄ precursors in aqueous solution. Upon annealing at 600 °C in air, an amorphous ZrO₂ nanoscale coating layer was obtained on the spinel nanoparticles with a particle size of <100 nm that formed from the splitting of the original spinel nanorods. The electrochemical cycling results clearly showed that nanoscale ZrO₂ coating significantly improved the rate capability and cycle life at 65 °C in spite of very high surface area of the spinel nanoparticles.     

Sequential injection lab-on-valve simultaneous spectrophotometric determination of trace amounts of copper and iron

A sequential injection (SI) method in a lab-on-valve (LOV) format for simultaneous spectrophotometric determination of copper and iron has been devised. The detection chemistry is based on the complex formation of 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]aniline (5-Br-PSAA) with copper(II) and/or iron(II) at pH 4.6. Copper(II) reacts with 5-Br-PSAA to form the complex which has an absorption maximum at 580 nm but iron(III) does not react. In the presence of a reducing agent only iron(II)-5-Br-PSAA complex is formed and detected at 558 nm. Under the optimum experimental conditions, the determinable ranges are 0.1-2 mg l⁻¹ for copper and 0.1-5 mg l⁻¹ for iron, respectively, with a sampling rate of 18 h⁻¹. The limits of detection are 50 μg l⁻¹ for copper and 25 μg l⁻¹ for iron. The relative standard deviations (n = 15) are 2% for 0.5 mg l⁻¹ copper and 1.8% for 0.5 mg l⁻¹ iron when determined in standard solutions. The recoveries range between 96 and 105% when determining 0.25-2 mg l⁻¹ of copper and 0.2-5 mg l⁻¹ of iron in artificial mixtures at copper/iron ratios of 1:10 to 5:1. The proposed SI-LOV method is successfully applied to the simultaneous determination of copper and iron in multi-element standard solution and in industrial wastewater samples.     

Rapid In Vitro Production of Cloned Plants of <Emphasis Type="Italic">Uraria picta</Emphasis> (Jacq.) DC—A Rare Medicinal Herb in Long-Term Culture

An efficient in vitro process for rapid production of cloned plants of Uraria picta has been developed employing nodal stem segments taken from field-grown plants. Explants showed bud-break followed by regeneration of shoots with restricted growth within 12 days on modified Murashige and Skoog’s medium supplemented with 0.25 mg l^–1 each of 6-benzylaminopurine and indole-3-acetic acid and 25 mg l^-1 adenine sulfate. Normal growth of shoots with good proliferation rate was achieved by reducing the concentrations of 6-benzylaminopurine and indole-3-acetic acid to 0.1 mg l^-1 each and incorporating 0.5 mg l^-1 gibberellic acid in the medium in which, on an average, 19.6 shoots per explant were produced. Further, during successive subcultures, increased concentrations of adenine sulfate (50 mg l^-l) and gibberellic acid (2 mg l^-l) along with the addition of 20 mg l^-l  dl-tryptophan were found conducive to control the problem of necrosis of shoots. In this treatment, several “crops” of shoots were obtained from single culture by repeated subculturing of basal portion of stalk in long-term. Isolated shoots rooted 100% in 0.25 mg l^-1 indole-3-butyric acid. In vitro-raised plants after hardening in inorganic salt solution grew normally in soil and came to flowering. Genetic fidelity of in vitro-raised plants was ascertained by rapid amplified polymorphic DNA (RAPD) markers. Also, quantitative estimation of two isoflavonones in their root extracts further confirmed true-to-type nature of plantlets.     

Profiling of the reactive oxygen species-related ecotoxicity of CuO, ZnO, TiO2, silver and fullerene nanoparticles using a set of recombinant luminescent Escherichia coli strains: differentiating the impact of particles and solubilised metals

We propose a novel combination of high-throughput luminescent bacterial tests for the evaluation of the reactive oxygen species (ROS)-generating potential of engineered nanoparticles (eNPs) and the role of solubilised metal ions in this process. The set of tests consists of differently engineered recombinant Escherichia coli strains: (1) a new sensor strain, which bioluminescence is induced by superoxide anions; (2) six recombinant E. coli strains (superoxide dismutase (sod) single, double and triple mutants and a respective wild-type strain), transformed with luxCDABE genes responding to toxic compounds by decreasing their luminescence; and (3) three strains in which bioluminescence is specifically induced by bioavailable metals (Cu, Zn and Ag). The applicability of this battery of tests in profiling oxidative potential of eNPs was evaluated on nTiO₂, nCuO, nZnO and nAg (25, 30, 70 and <100 nm, respectively) NPs and fullerenes. As controls for the size or solubility, the bulk formulations (bTiO₂, bCuO and bZnO) and soluble salts (ZnSO₄, CuSO₄ and AgNO₃) were also analysed. Bacterial toxicity tests showed that nCuO was four-fold more toxic, and nAg was 15-fold more toxic to triple sod mutant than to wild type (2-h EC₅₀ values were 8.1 and 2.0 mg Cu l⁻¹, respectively, and 46 and 3.1 mg Ag l⁻¹, respectively). Formation of ROS by nCuO and nAg was proved by superoxide anion-inducible strain. The metal sensor bacteria showed that the ROS formation by CuO NPs was caused by solubilised Cu ions, but in case of nAg, particles also had an effect. nZnO was remarkably more toxic to sod triple mutant than to wild type strain (2-h EC₅₀ were 4.5 and 54 mg Zn l⁻¹, respectively). Fullerenes inhibited the bioluminescence of sod triple mutant at 3,882 mg l⁻¹ but had no effect on the wild-type strain even at 20,800 mg l⁻¹. Nano and bTiO₂ showed some effect on viability of bacteria only at high concentrations (>4,000 mg l⁻¹) although nTiO₂ (but not bTiO₂) induced the bioluminescence of the superoxide anion sensing bacteria starting from 100 mg l⁻¹. Thus, our innovative combined approach is expected to provide more consistent and informative data concerning the general toxicity, ROS-production potential and also solubilisation of metals in the case of metallic NPs.     

Synthesis of gold/polydopamine composite surfaces on glass substrates for localized surface plasmon resonance and catalysis

Composite materials of polydopamine (PDA) and gold nanoparticles on glass substrates (Au/PDA@slide) were obtained via a simple chemical process. First, PDA films (PDA@slide) were formed by immersing slides in 20 mg ml⁻¹ dopamine aqueous solution at pH = 8.5 for 1 h. Then, PDA@slide was dipped in 0.02 M chloroauric acid (HAuCl₄) aqueous solution for a certain time, Au/PDA@slide being formed. Gold nanoparticles were obtained by the reductive properties of PDA. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. The catalytic properties of Au/PDA@slide were evaluated using the reduction of 4‐nitrophenol (4‐NP) in the presence of sodium borohydride (NaBH₄) aqueous solution at room temperature. The catalytic activity of the optimal Au/PDA@slide was so satisfactory that the reduction of 4‐NP was completed within 10 min. Moreover, the Au/PDA@slide composite material was stable up to five cycles without significant loss of its catalytic activity. In addition, Au/PDA@slide also exhibited photocatalytic ability, photodegrading 2.5 ml of 17.5 mg l⁻¹ methyl orange in 100 min. By measuring the UV–visible absorption bands of Au/PDA@slide, it was proved that the condition of the strongest surface plasmon resonance of Au/PDA@slide was the optimal condition for catalytic reduction of 4‐NP.     

Electrochemical corrosion behavior of nanocrystalline zinc coatings in 3.5% NaCl solutions

The corrosion behavior of electrodeposited nanocrystalline (NC) zinc coatings with an average grain size of 43 nm was investigated in 3.5% NaCl solutions in comparison with conventional polycrystalline (PC) zinc coatings by using electrochemical measurement and surface analysis techniques. Both polarization curve and electrochemical impedance spectroscopy (EIS) results indicate that NC and PC coatings are in active state at the corrosion potentials, and NC coatings have much higher corrosion resistance than PC ones. The corrosion products on both coating surfaces are mainly composed of ZnO and Zn₅(OH)₈Cl₂·H₂O, but the corrosion products can form a relatively more protective layer on NC coating surfaces than on PC coatings. The EIS characteristics and corrosion processes of PC and NC zinc coatings during 330 h of immersion were discussed in detail.     

Optimization of cadmium adsorption from aqueous solutions by functionalized graphene and the reversible magnetic recovery of the adsorbent using response surface methodology

Novel functionalized graphene adsorbent was prepared and characterized using different techniques. The prepared adsorbent was applied for the removal of cadmium ions from aqueous solution. A response surface methodology was used to evaluate the simple and combined effects of the various parameters, including adsorbent dosage, pH, and initial concentration. Under the optimal conditions, the cadmium removal performance of 70% was achieved. A good agreement between experimental and predicted data in this study was observed. The experimental results revealed of cadmium adsorption with high linearity follow Langmuir isotherm model with maximum adsorption capacity of 502 mg g^?1, and the adsorption data fitted well into pseudo‐second order model. Thermodynamic studies showed that adsorption process has exothermic and spontaneous nature. The recommended optimum conditions are: cadmium concentration of 970 mg L^?1, adsorbent dosage of 1 g L^?1, pH of 6.18, and T = 25 °C. The magnetic recovery of the adsorbent was performed using a magnetic surfactant to form a noncovalent magnetic functionalized graphene. After magnetic recovery of the adsorbent both components (adsorbent and magnetic surfactant) were recycled by tuning the surface charges through changing the pH of the solution. Desorption behavior studied using HNO₃ solution indicated that the adsorbent had the potential for reusability.     

A multisyringe sequential injection method for monitoring water in the energy cogeneration system of a municipal waste incinerator

Leading-edge urban solid waste ashing plants use burning heat energy to obtain electrical power. Water fed to their boilers for conversion into steam should be highly pure in order to minimize corrosion, scaling and similar phenomena, which can lead to malfunctioning and a reduced useful life but can be avoided by proper management and control of the water supply. In this work, we developed a multiparameter monitor based on multisyringe sequential injection for the sequential determination of up to eight important parameters, namely: pH, specific and acid conductivity, hydrazine, ammonium, phosphate, silicate and total iron.Acid conductivity was determined by passing the sample through a cation-exchange resin in order to retain ammonium ion and release protons. This parameter was deemed the most accurate indicator of dissolved solids in boiler water. Chemical parameters were determined spectrophotometrically: hydrazine by reaction with p-dimethylaminobenzaldehyde, ammonium by the modified Berthelot reaction, iron with o-phenanthroline, and phosphate and silica by formation of a molybdoheteropoly blue dye in the presence of ascorbic acid as reductant. Use of the optimum chemical and physical operating conditions provided 3s_blank detection limits of 0.01 mg l⁻¹ N₂H₄, 0.13 mg l⁻¹ NH₄⁺, 0.04 mg l⁻¹ Fe, 0.03 mg l⁻¹ SiO₂ and 0.05 mg l⁻¹ PO₄³⁻, and relative standard deviations not greater than 2.5%. The methods integrated in the proposed monitor were successfully applied to real samples from the water-steam cycle at the Son Reus ashing plant in Palma de Mallorca (Spain).     

Solvent/substrate effects on the micelle-catalyzed aquation of some iron(II)-phenanthroline complexes, II. Influence of urea and sodium benzoate on the aquation of Fe(Ph2Phen)32+ in acetone

The micelle-catalyzed aquation rates of iron(II) phenanthroline complex Fe(Ph₂Phen) ₃ ²⁺ have been measured in aqueous acetone as solvent in the presence of urea and sodium benzoate as substrates. The variation patterns manifested by the estimated maximum catalytic factors and k_o vs [substrate] profiles show that the aquation rates of the complex are inhibited by urea, while they are significantly enhanced by sodium benzoate. These observations have been radionalized by considering the relative micelle bond-breaking capacities of the substrates, the relative strengths of the H-bonds formed by the substrate/OH^– headgroups of the micelle and the H₂O/OH^– headgroups of the micelle pairs.     

Semiconductor properties of nanocrystalline diamond electrodes

The semiconductor properties of nitrogenated nanocrystalline diamond electrodes and their corrosion transformations caused by electrochemical experiment in indifferent electrolyte (1 M K₂SO₄) were studied by the electrochemical impedance spectroscopy method. It was shown that after electrochemical measurements a narrow diamond peak at 1335.7 cm^?1 appears in the Raman spectrum; formerly the peak was hidden at a background of the intense signal inherent to graphite-like carbon. It was suggested that the corrosion damage caused by the exposure to electrochemical experiment resulted in a decrease of relative amount of nondiamond (graphite-like) carbon in the subsurface layer in the nanocrystalline diamond. By using Mott-Schottky plots, the nanocrystalline diamond was shown having n-type conductance. Within the bounds of the “effective medium” approach, the nanocrystalline diamond’s flat-band potential in aqueous solution and the noncompensated donor apparent concentration were estimated.     

Immersion enthalpy and the constants of Langmuir model in the 3-chloro phenol adsorption on activated carbon

The adsorption process of 3-chloro phenol from aqueous solution on a activated carbon prepared from African palm stone and which presents a specific surface area of 685 m² g⁻¹, a greater quantity of total acid groups and a pH_PZC of 6.8 is studied. The adsorption isotherms are determined at pH values of 3, 5, 7, 9 and 11. The adsorption isotherms are fitted to the Langmuir model and the values of the maximum quantity adsorbed that are between 96.2 and 46.4 mg g⁻¹ are obtained along with the constant K_L with values between 0.422 and 0.965 L mg⁻¹. The maximum quantity adsorbed diminishes with the pH and the maximum value for this is a pH of 5. The immersion enthalpies of the activated carbon in a 3-chloro phenol solution of constant concentration, of 100 mg L⁻¹, are determined for the different pH levels, with results between 37.6 and 21.2 J g⁻¹. Immersion enthalpies of the activated carbon in function of 3-chloro phenol solution concentration are determined to pH 5, of maximum adsorption, with values between 28.3 and 38.4 J g⁻¹, and by means of linearization, the maximum immersion enthalpy is calculated, with a value of 41.67 J g⁻¹. With the results of the immersion enthalpy, maximum quantity adsorbed and the constant K_L, establish relations that describe the adsorption process of 3-chloro phenol from aqueous solution on activated carbon.     

A high performance nano-structure conductive coating on a Crofer22APU alloy fabricated by a novel spinel powder reduction coating technique

A nano-structure conductive coating was fabricated on a Crofer22APU alloy interconnect by an original coating strategy using Mn_0.9Y_0.1Co₂O₄ (MYC) novel spinel nanocrystalline powder. A unique treatment method by which the spinel powder was reduced was used to prepare the green coating. The resulting coating was about 12 μm in thickness, and was composed of MYC nanocrystalline with an average particle size of about 100 nm. The coating was well adhered with the substrate alloy. Less than 4 mΩ cm² of the area specific resistance (ASR) was obtained, and no obvious degradation was observed for a coated alloy (whose coating thickness was about 30 μm) after operated at 800 °C for 538 h under seven thermal cyclings. The coated alloy exhibited excellently electrical performance and long-term stability compared with the uncoated one. The exploration of the novel spinel powder reduction coating technique for alloy interconnect to obtain cheap coatings with excellent microstructure and performance showed a promising prospect for the practical application of solid oxide fuel cells (SOFCs).     

Influence of formulation method and related processes on structural,electrical and electrochemical properties of LMS/NCA-blend electrodes

The impact of different formulation methods, involving related process technologies, as well as the influence of dispersing intensity on the structural and electrical coating layer properties of LiMn₂O₄/LiNi_0,80Co_0,15Al_0,05O₂ (LMS/NCA) blends are studied. Findings are finally correlated with the electrochemical rate-capability in order to derive process-structure–property functions to facilitate systematical electrode development. LMS was found to be sensitive according mechanical stress but by processing LMS/NCA blend electrodes this problem can be avoided. In general carbon black (CB) agglomerate size and its distribution in the binder network were identified to be significant factors influencing rate-capability. Both were found to influence pore structure by utilizing representative low and high energy methods for the formulation of the suspensions. The specific pore volume in the pore size region of 10 μm ≥ d_p ≥ 0.5 μm was discovered to strongly influence rate-capability. These highways for lithium-ion transport allow for higher mass of lithium-ions per unit time penetrating into the inner surface of the coating layer. Specific volume and thus rate-performance can either be increased by a binder solution based formulation method or by decreasing the specific energy input during dispersing process. Hence no superior formulation method exists. The adjustment of mixing intensity and therewith the achieved CB agglomerate size, referring to the formulation method used, is essential. Thus comparable electrochemical rate performance was found for the same specific volume of approximately 0.25 cc g⁻¹ but for different dispersing intensities. Further, the pore size region of 1.5 μm > d_p > 0.03 μm was identified to be characteristic for the CB agglomerate size and the corresponding CB treatment method used. Peakedness of the pore size distribution was found to follow electrode conductivity which was the largest for a distributive dry mixing method. For electrodes showing a good CB agglomerate distribution in the binder network rate-capability was found to be limited by the pore structure of the coating layer and, thus, preliminarily by the corresponding ion transport kinetic. Based on the findings a model concept on processes occurring during dispersing was proposed and discussed to describe viscosity evolution over dispersing time.     

Poly(2,5-dimethoxyaniline) film coating for corrosion protection of iron

A poly(2,5-dimethoxyaniline) (PDMA) film was coated on the iron surface by the electropolymerization of 2,5-dimethoxyaniline in neutral buffer solution (pH?6.86). The PDMA film strongly adhered to the surface because of the polar methoxy groups of the PDMA molecules. The fact that no electrochemical response of the PDMA film-coated iron electrode to dissolved Fe²⁺ exhibited that the PDMA film was less permeable to dissolved species, acting as a diffusion barrier against agents causing corrosion such as H₂O and O₂. The PDMA film coating greatly lowered the anodic current peak ascribed to the anodic dissolution of iron and the corrosion current in strongly acidic medium, 0.5?M H₂SO₄ aqueous solution (1?M?????mol?dm^??) as well as neutral medium (pH?6.86). The high anti-corrosion ability was due to a hybrid effect of the PDMA film not only as the diffusion barrier, but also as an in situ oxidant in spite of the slight redox activity of PDMA. In addition, the PDMA film is much more durable and adhesive than polyaniline film against over-oxidation.