Behavior of (La,Sr)CoO3- and La2NiO4-based ceramic anodes in alkaline media: compositional and microstructural factors

The behavior of dense ceramic anodes made of perovskite-type (x = 0.30–0.70; y = 0–0.05; z = 0–0.20) and K₂NiF₄-type (Me = Co, Cu; x = 0–0.20) indicates significant influence of metal hydroxide formation at the electrode surface on the oxygen evolution reaction (OER) kinetics in alkaline solutions. The overpotential of cobaltite electrodes was found to decrease with time, while cyclic voltammetry shows the appearance of redox peaks characteristic of Co(OH)₂/CoOOH. This is accompanied with increasing effective capacitance estimated from the impedance spectroscopy data, because of roughening of the ceramic surface. The steady-state polarization curves of in the OER range, including the Tafel slope, are very similar to those of model Co(OH)₂–La(OH)₃ composite films where the introduction of lanthanum hydroxide leads to decreasing electrochemical activity. La₂NiO₄-based anodes exhibit a low electrochemical performance and poor stability. The effects of oxygen nonstoichiometry of the perovskite-related phases are rather negligible at high overpotentials but become significant when the polarization decreases, a result of increasing role of oxygen intercalation processes. The maximum electrocatalytic activity to OER was observed for A-site-deficient , where the lanthanum content is relatively low and the Co⁴⁺ concentration determined by thermogravimetric analysis is highest compared to other cobaltites. Applying microporous layers made of template-synthesized nanocrystalline leads to an improved anode performance, although the effects of microstructure and thickness are modest, suggesting a narrow electrochemical reaction zone. Further enhancement of the OER kinetics can be achieved by electrodeposition of cobalt hydroxide- and nickel hydroxide-based films. Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.     

Mixed-Valence 24-Vanadophosphate Decorated with Six RuII(dmso)3 Groups: [{RuII3(dmso)9PVV11VIVRuIIIO37(OH)3}2]8?

The mixed-valence 24-vanadophosphate (1) has been synthesized and characterized in the solid state by IR, magnetism, EPR, XPS, and elemental analysis. Single-crystal X-ray analysis was carried out on (Na-1), which crystallizes in the triclinic system, space group , with a = 17.168(3) ?, b = 18.1971(14) ?, c = 20.1422(13) ?, α = 114.753(3)°, β = 99.390(4)°, γ = 95.124(4)°, and Z = 2. Polyanion 1 has an unusual, open structure composed of 2 Ru^IIIO₆ octahedra, 2 V^IVO₆ octahedra, 14 V^VO₅ square-pyramids, 8 V^VO₄ tetrahedra, and 2 PO₄ tetrahedra which are all directly linked via edges and corners. The outer surface of 1 is decorated with six Ru^II(dmso)₃ groups. XPS studies on Na-1 confirm the presence of 2 Ru^III and 6 Ru^II as well as 22 V^V and 2 V^IV centers. Magnetic susceptibility data on Na-1 show that the V^IV–Ru^III pairs are coupled antiferromagnetically, with J ₁ = −13 K and J ₂ ∼ −3 K. We did not detect any peak in our EPR measurements on Na-1, thus supporting the conclusion that Na-1 is diamagnetic in its ground state. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. In Memoriam Prof. F. A. Cotton     

Properties and performance of BaxSr1−xCo0.8Fe0.2O3−δ materials for oxygen transport membranes

The present paper discusses the oxygen transport properties, oxygen stoichiometry, phase stability, and chemical and mechanical stability of the perovskites (BSCF) and (SCF) for air separation applications. The low oxygen conductive brownmillerite phase in SCF is characterized using in-situ neutron diffraction, thermographic analysis and temperature programmed desorption but this phase is not present for BSCF under the conditions studied. Although both materials show oxygen fluxes well above 10 ml/cm²·min at T=1,273 K and pO₂=1 bar for self-supporting, 200 μm-thick membranes, BSCF is preferred as a membrane material due to its phase stability. However, BSCF’s long-term stable performance remains to be confirmed. The deviation from ideal oxygen stoichiometry for both materials is high: δ>0.6. The thermal expansion coefficients of BSCF and SCF are 24×10⁻⁶ and 30×10⁻⁶ K⁻¹, respectively, as determined from neutron diffraction data. The phenomenon of kinetic demixing has been observed at pO₂<10⁻⁵ bar, resulting in roughening of the surface and enrichment with alkaline earth metals. Stress–strain curves were determined and indicated creep behavior that induces undesired ductility at T=1,073 K for SCF. Remedies for mechanical and chemical instabilities are discussed.     

Oxygen permeation and stability of Zr0.8Y0.2O0.9‒La0.8Sr0.2CrO3-δ dual-phase composite

A tubular membrane made of Zr_0.8Y_0.2O_1.9 (60 vol%) and was prepared by a standard ceramic process. Oxygen permeation through the membrane tube was examined by exposing its outer shell to air and sweeping its inner wall with pure helium or CO balanced with helium. An oxygen flux of 9.2×10⁻⁹ mol cm⁻² s⁻¹ was measured at 950°C under air/He gradient, and a larger flux of 3.2×10⁻⁸ mol cm⁻² s⁻¹ at 930°C under air/CO gradient. The membrane tube was found to exhibit excellent stability under highly reducing atmosphere and elevated temperatures. The oxygen permeation rate is likely to be increased through the modification of the surface and reduction of the membrane thickness.     

Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol by bis(hydrogen periodato)argentate(III) complex anion: a kinetic study

Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol (MPPD) by bis(hydrogenperiodato) argentate(III) complex anion, [Ag(HIO₆)₂]⁵⁻ has been studied in aqueous alkaline medium by use of conventional spectrophotometry. The major oxidation product of MPPD has been identified as 3-(4-methoxyphenoxy)-2-ketone-1-propanol by mass spectrometry. The reaction shows overall second-order kinetics, being first-order in both [Ag(III)] and [MPPD]. The effects of [OH⁻] and periodate concentration on the observed second-order rate constants k′ have been analyzed, and accordingly an empirical expression has been deduced:

Binuclear cobalt(II/II) and cobalt(II/III) chelates with O<Subscript>2</Subscript>N<Subscript>2</Subscript> ligands: synthesis,structure and magnetic studies

Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)₂·4H₂O with H₂L¹ and H₂L², respectively, in acetonitrile solution. Here, [L¹]²⁻ and [L²]²⁻ are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of and were determined by x-ray crystallography. In , each cobalt atom has distorted trigonal bipyramid geometry, while in , each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in . The magnetic characterization for is in agreement with the presence of Co(II) and Co(III) centers. Graphical Abstract  The title complexes and have been synthesized in excellent yields by reacting Co(OAc)₂·4H₂O with dianionic N₂O₂ coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III) centers. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Etude par Spectrophotometrie d'absorption de l'Equilibre Pu4++Cl−⇋Pu3++1/2 Cl2 dans le melange LiCl−KCl (70–30% mol) fondu

The quantitative study of the equilibrium Pu⁴⁺+Cl⁻⇋Pu³⁺+1/2 Cl₂ in LiCl−KCl (70–30% mol) at 455, 500, 550 and 600°C by visible and near I.R. absorption spectrophotometry allows the calculation of the reaction's equilibrium constant, the mean thermodynamic data ΔH=27±14 kJ·mol⁻¹ and ΔS=37±17 J·mol⁻¹·K⁻¹ and the standard potential of the couple .      

Hydrogen peroxide as a reductant of hexacyanoferrate(III) in alkaline solutions: kinetic studies

The kinetics of hexacyanoferrate(III) reduction by hydrogen peroxide in strongly alkaline media leading to hexacyanoferrate(II) ion have been studied spectrophotometrically within the wavelength range 300–500 nm. The reaction obeys a simple pseudo-first-order rate expression under the applied conditions, namely, a large excess of the reductant and OH⁻ anion concentrations, and a low oxidant concentration. The linear dependences of the pseudo-first-order rate constant on OH⁻ and H₂O₂ concentrations are consistent with the rate law of the form: where and are the second- and the pseudo-third-order rate constants for the electron transfer from HO₂ ⁻ and O₂ ²⁻ to [Fe(CN)₆]³⁻, respectively. The apparent activation parameters determined at 0.4 M NaOH are as follows: ΔH ^# = (18.0 ± 1.0) kJ mol⁻¹ and ΔS ^# = (−155 ± 3.5) J K⁻¹ mol⁻¹. The possible mechanism of the reaction is discussed.     

Improvement of the electrochemical properties of “as-grown” boron-doped polycrystalline diamond electrodes deposited on tungsten wires using ethanol

The electrochemical properties of boron-doped diamond (BDD) polycrystalline films grown on tungsten wire substrates using ethanol as a precursor are described. The results obtained show that the use of ethanol improves the electrochemistry properties of “as-grown” BDD, as it minimizes the graphitic phase upon the surface of BDD, during the growth process. The BDD electrodes were characterized by Raman spectroscopy, scanning electronic microscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The boron-doping levels of the films were estimated to be ∼10²⁰ B/cm³. The electrochemical behavior was evaluated using the and redox couples and dopamine. Apparent heterogeneous electro-transfer rate constants were determined for these redox systems using the CV and EIS techniques. values in the range of 0.01–0.1 cm s⁻¹ were observed for the and redox couples, while in the special case of dopamine, a lower value of 10⁻⁵ cm s⁻¹ was found. The obtained results showed that the use of CH₃CH₂OH (ethanol) as a carbon source constitutes a promising alternative for manufacturing BDD electrodes for electroanalytical applications.     

Palladized aluminum as a novel substrate for electrosynthesis of polyaniline in sulfuric acid solutions

The electropolymerization of aniline on a palladized aluminum electrode (Pd/Al) by potentiodynamic as well as potentiostatic methods is described. The effect of the monomer concentration between 0.01 and 0.4 M on the polyaniline (PANI) formation and its growth on the Pd/Al electrode was investigated and a suitable concentration of 0.2 M is suggested. A similar study was carried out to investigate the effect of sulfuric acid concentration and 0.1 M sulfuric acid was chosen. A study on the influence of electropalladization time on the polymer formation and its growth suggested a convenient time of 40 s. The stability of the PANI film on the Pd/Al electrode was studied as function of the potential imposed on the electrode. For applied electrode potentials of 0.1–0.7 V, the first-order degradation rate constant, k, of PANI film varies between 1×10⁻⁶ and 2×10⁻⁵ s⁻¹, and a relatively low slope (i.e., 2.2) was obtained for the plot of log k versus E. The coatings were characterized by scanning electron microscopy (SEM), and cyclic voltammetric behavior of the PANI-deposited Pd/Al electrode is discussed. The electrocatalytic activity of the PANI-deposited Pd/Al electrode against para-benzoquinone/hydroquinone (Q/H₂Q) and redox systems were investigated and on the basis of of the corresponding cyclic voltammograms and the redox systems were identified as the reversible and quasi-reversible systems, respectively.     

Removal of Nitrogen and Organic Matter in a Radial-Flow Aerobic-Anoxic Immobilized Biomass Reactor Used in the Posttreatment of Anaerobically Treated Effluent

This work reports on the removal of organic matter and nitrogen in a radial-flow aerobic-anoxic immobilized biomass (RAIB) reactor fed with domestic sewage pretreated in a horizontal-flow anaerobic immobilized biomass (HAIB) reactor. Polyurethane foam was used as support material for biomass attachment in both reactors. In batch experiments, a first-order kinetic model with residual concentration represented the organic matter removal rate, whereas nitrogen conversion followed a pseudo-first-order reaction in series model, with kinetic constants k ₁ (ammonium to nitrite) and k ₂ (nitrite to nitrate) of 0.25 and 6.62 h⁻¹, respectively. The RAIB reactor was operated in continuous-flow mode and changes in the airflow rate and hydraulic retention time were found to interfere in the apparent kinetic constants to the nitritation (k ₁) and nitratation (k ₂). Nitrification and denitrification were achieved in the partially aerated RAIB reactor operating with hydraulic retention times of 3.3 h and 2.7 h in the aerobic and anoxic zones, respectively. Ethanol was added in the anoxic zone of the reactor to promote denitrification. The effluent flow of the RAIB reactor presented a COD of 52 mg l⁻¹, and concentrations of 2 mg , 1.24 mg and 3.46 mg .     

Mechanical properties of mixed conducting La0.5Sr0.5Fe1−x Co x O3−δ (0≤x≤1) materials

Young’s modulus, strain–stress behavior, fracture strength, and fracture toughness of (0≤×≤1) materials have been investigated in the temperature range 20–1,000°C. Young’s moduli of and , measured by resonant ultrasound spectroscopy, were 130±1 and 133±3 GPa, respectively. The nonlinear stress–strain relationship observed by four-point bending at room temperature was inferred as a signature of ferroelastic behavior of the materials. Above the ferroelastic to paraelastic transition temperature, the materials showed elastic behavior, but due to high-temperature creep, a nonelastic respond reappeared above ∼800°C. The room temperature fracture strength measured by four-point bending was in the range 107–128 MPa. The corresponding fracture toughness of , measured by single edge V-notch beam method, was 1.16±0.12 MPa·m^1/2. The measured fracture strength and fracture toughness were observed to increase with increasing temperature. The fracture mode changed from intragranular at low temperature to intergranular at high temperature. Tensile stress gradient at the surface of the materials caused by a frozen-in gradient in the oxygen content during cooling was proposed to explain the low ambient temperature fracture strength and toughness.     

Studies on structure and electrochemical properties of pillared M–MnO<Subscript>2</Subscript> (M=Ba<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, ZrO<Superscript>2+</Superscript>)

Supramolecular pillared oxides were prepared through the intercalation of M²⁺ cations into a MnO₂ host matrix by the method of ion exchange between the precursor δ-K _x MnO₂ and the corresponding guest. The materials M-MnO₂ crystallize in the hexagonal system, the same structure as the precursor, with a larger interlamellar spacing. In the case of ZrO-MnO₂, extended X-ray absorption fine structure (EXAFS) determination indicates that the Zr atom locates between the MnO₂ layers forming a stable structure. Compared with the precursor, the cycling property of M-MnO₂ was improved distinctly, while the capacity decreased to some degree due to the strong interaction between pillars and the host matrix. Among these pillared materials, ZrO-MnO₂ has an advanced reversible capacity of 161.5 mAh·g⁻¹ and improved cycling behavior compared with the precursor.     

Oxygen transport in La0.5Sr0.5Fe1−yTiyO3−δ (y=0.0, 0.2) membranes

The influence of partial substitution of Fe with Ti on the oxygen transport properties of La_1−x Sr _x FeO₃ membranes was investigated in view of their application for oxygen separation. Samples of composition (y=0, 0.2) were prepared and their oxygen transport properties characterised by potential step relaxation and by oxygen permeation measurement in an air/argon gradient. With the first technique, chemical diffusion and surface exchange (k _S) coefficients were obtained by fitting of the current relaxation data to a single expression valid over the complete time range. The Ti-substituted composition gave slightly larger values of and k _S. The trend was opposite for the measured oxygen permeation flux. In the latter experience, ordering of oxygen vacancies was observed at lower temperature, reducing significantly the performance of the material.     

Kinetics and mechanism of oxidation of hydroxylamine by tetrachloroaurate(III) ion

The oxidation of H₂NOH is first-order both in [NH₃OH⁺] and [AuCl₄ ^–]. The rate is increased by the increase in [Cl^–] and decreased with increase in [H⁺]. The stoichiometry ratio, [NH₃OH⁺]/[AuCl₄ ^–], is 1. The mechanism consists of the following reactions.

Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C

The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO₃, KBr, KI, KNO₃, CaCl₂, SrCl₂, BaCl₂, Li₂SO₄, K₂SO₄, Mn(NO₃)₃)] as a function of concentration at 25°C. The solubilities, mol (kg-H₂O)^–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg^–1)

Kinetics of the uninhibited and ethanol-inhibited CoO,Co<Subscript>2</Subscript>O<Subscript>3</Subscript> and Ni<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyzed autoxidation of sulfur(IV) in alkaline medium

For getting an insight into the mechanism of atmospheric autoxidation of sulfur(IV), the kinetics of this autoxidation reaction catalyzed by CoO, Co₂O₃ and Ni₂O₃ in buffered alkaline medium has been studied, and found to be defined by Eqs. I and II for catalysis by cobalt oxides and Ni₂O₃, respectively.

Mechanism of the catalyzed by cysteine electroreduction of the insoluble in water cobalt(II) salt as a component of carbon paste electrode

The mechanism of the Co(II) catalytic electroreduction of water insoluble CoR₂ salt in the presence of cysteine was developed. CoR₂ = cobalt(II) cyclohexylbutyrate is the component of a carbon paste electrode. Electrode surface consecutive reactions are: (a) fast (equilibrium) reaction of the complex formation, (b) rate-determining reversible reaction of the promoting process of CoR(Ac⁺) complex formation, (c) rate-determining irreversible reaction of the electroactive complex formation with ligand-induced adsorption, and (d) fast irreversible reaction of the electroreduction. Reactions (a,b) connected with CoR₂ dissolution and reactions (c,d) connected with CoR₂ electroreduction are catalyzed by . Regeneration of (reactions “b,d”) and accumulation of atomic Co(0) (reaction “d”) take place. Experimental data [Sugawara et al., Bioelectrochem Bioenergetics 26:469, 1991]: i _a vs E (i _a is anodic peak, E is cathodic accumulation potential), i _a vs , and i _a vs pH have been quantitatively explained.     

Simple and rapid catalytic spectrophotometric determination of superoxide anion radical and superoxide dismutase activity in natural medical vegetables using phenol as the substrate for horseradish peroxidase

The coupling reaction of 4-aminoantipyrine (4-AAP) with phenol using the superoxide anion radical ( ) as oxidizing agent under the catalysis of horseradish peroxidase (HRP) was studied. Based on the reaction, produced by irradiating vitamin B₂ (V_B2) was spectrophotometrically determined at 510 nm. Under the optimum experimental conditions, the relationship between A ₅₁₀ and concentration was linear in the range 9.14×10^–6–1.2×10^–4 mol L^–1. The detection limit was determined to be 1.37×10^–6 mol L^–1. A possible reaction mechanism was discussed. The effect of interferences and surfactants on the determination of was also investigated. The proposed method was applied to determine superoxide dismutase activity in garlic, scallion, and onion with satisfactory results.     

Nickel surface anodic oxidation and electrocatalysis of oxygen evolution

The processes of nickel surface anodic oxidation taking place within the range of potentials preceding oxygen evolution reaction (OER) in the solutions of 1 M KOH, 0.5 M K₂SO₄, and 0.5 M H₂SO₄ have been analyzed in the present paper. Metallic nickel, thermally oxidized nickel, and black nickel coating were used as Ni electrodes. The methods of cyclic voltammetry and X-ray photoelectron spectroscopy were employed. The study was undertaken with a view to find the evidence of peroxide-type nickel surface compounds formation in the course of OER on the Ni electrode surface. On the basis of experimental results and literature data, it has been suggested that in alkaline solution at E ≈ 1.5 V (RHE) reversible electrochemical formation of Ni(IV) peroxide takes place according to the reaction as follows: This reaction accounts for both the underpotential (with respect to ) formation of O₂ from NiOO₂ peroxide and also small experimental values of dE/dlgi slope (<60 mV) at low anodic current densities, which are characteristic for the two-electron transfer process. It has been inferred that the composition of the γ-NiOOH phase, indicated in the Bode and revised Pourbaix diagrams, should be ∼5/6 NiOOH + ∼1/6 NiOO₂. The schemes demonstrating potential-dependent transitions between Ni surface oxygen compounds are presented, and the electrocatalytic mechanisms of OER in alkaline, acid, and neutral medium have been proposed.