Effects of Sr/Ti-ratio in SrTiO3-based SOFC anodes investigated by the use of cone-shaped electrodes

In this work the A-site deficiency limit for undoped SrTiO₃, calcined in air or reducing atmosphere, was investigated. XRD and SEM analyses showed that when using the solid-state synthesis route it was difficult to achieve any A-site deficiency. Even very small deviations from unity in the Sr/Ti-ratio resulted in impurity phases. The effects of Sr/Ti-ratio on the performance of SrTiO₃ anodes for solid oxide fuel cells (SOFCs) was investigated by impedance spectroscopy with cone-shaped electrodes. The electrocatalytic activity of the SrTiO₃ cone samples, with various amount of reduced titanium dioxide phases (Magnéli phases), was investigated for oxidation of H₂ at 700 °C. High temperature treatment at 1000 °C, between the measurements at 700 °C, showed that high content of Magnéli phases leads to faster degradation of the activity. The suitability for using cone-shaped electrodes as a tool for investigating electrode materials is discussed.     

Nile blue adsorbed onto silica gel modified with niobium oxide for electrocatalytic oxidation of NADH

A study of modified carbon paste electrode employing Nile blue (NB) adsorbed on silica gel modified with niobium oxide (SN) for electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH) is described. The adsorbed organic dye on SN was used to prepare a modified carbon paste electrode to investigate its electrochemical properties. The formal potential (E°′) of the adsorbed NB (−230 mV vs. saturated calomel electrode, SCE) showed a shift of 70 mV towards a more positive potential value, compared to NB dissolved in aqueous solution. In solutions with pH between 6.0 and 8.0 did stability and E°′ remained almost constant. However, for a solution pH lower than 6.0 the E°′ was affected by the acidity of the contacting solution, shifting the E°′ towards more positive values. For the solution pHs between 6.0 and 8.0 the electrocatalytic activity remained almost constant. A linear response range for NADH between 1.0×10⁻⁵ and 5.2×10⁻⁴ mol l⁻¹, at pH 7.0, was observed for the electrode, with an applied potential of −200 mV versus SCE. The formation of an intermediate charge transfer (CT) complex was proposed to the CT reaction between NADH and adsorbed NB. The heterogeneous electron transfer rate, k_obs, was 1400 M⁻¹ s⁻¹ and the apparent Michaelis-Menten constant, was 0.21 mM at pH 7.0 evaluated from rotating disk electrode (RDE) experiments with an electrode coverage of about 5.2×10⁻⁹ mol cm⁻². The increase in the reaction rate between NADH and the immobilized NB compared to those obtained with dissolved NB was assigned to the shift of the E°′ towards more positive values.     

Activity of gold towards methylamine electrooxidation

The kinetics of methylamine oxidation at a gold electrode in contact with an alkaline electrolyte solution was studied. The adsorptive behaviour of substrate molecules was determined by changes in the differential capacitance of the double layer at the electrode/solution interface. The electrooxidation of methylamine occurs only in the potential range of gold oxide layer formation. The general reaction pathways of methylamine oxidation on the gold electrode is proposed.     

三维电极电解阴离子表面活性剂废水的研究

采用三维电极电解法对含阴离子表面活性剂（LAS）废水的处理进行了研究，考察了不同电极组合、槽电压、停留时间、电极间距及废水的pH值对降解效果的影响，并对电解机理作了初步探讨.实验表明：LAS废水处理的最佳工艺为：极间距2cm，槽压为8V，电解时间为40min.LAS、COD、TOC的去除率分别在94.5%、66.2%和58.7%以上.电极材料对去除率有很大影响.     

Accumulation of Cu(II) cations in poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions and its application in Cu-selective electrodes with PVC based membranes

Electrochemical properties of poly(3,4-ethylenedioxythiophene) doped with hexacyanoferrate(II,III) ions (PEDOT(HCF)) were studied in the presence of Cu²⁺ ions. Voltammetric and EDAX studies revealed retention of hexacyanoferrate anions in the polymer film and accumulation of Cu(II) cations, as well as formation of solid copper hexacyanoferrate near the polymer surface.Accumulation of Cu²⁺ ions was found to be advantageous from the point of view of PEDOT(HCF) applications as a solid contact (ion-to-electron transducer) in all-solid-state Cu²⁺-selective electrodes with solvent polymeric polyvinyl chloride (PVC) based membrane, containing Cu²⁺-selective ionophore. Binding of Cu²⁺ ions in the conducting polymer layer results in analyte ions flux into the transducer phase. Thus, pronounced enhancement of selectivity of the all-solid-state Cu²⁺-selective electrode or lower detection limit of the potentiometric response range was achieved, reaching under optimised conditions 10⁻⁷ M CuSO₄.     

Electropolymerization of chlorinated phenols on a Pt electrode in alkaline solution. Part II: An electrochemical quartz crystal microbalance study

Electropolymerization of phenol and mono-, di-, tri-, pentachlorophenols was studied using EQCM on a Pt electrode at 0.78 V (SHE) in 1 M NaOH solution containing 0.1 M of the corresponding phenol. The highest electropolymerization rate was found for ortho-substituted chlorophenols indicating a weak fouling of the electrode. Low electropolymerization rates for para-substituted chlorophenols suggest a low permeability of the polymer film, resulting in rapid electrode fouling. The EQCM data suggest that electropolymerization of chlorophenols occurs without Cl-elimination for the monomers with unsubstituted ortho and para positions. Dechlorination is most pronounced for electropolymerization of para-substituted isomers. The mechanism of electropolymerization of chlorophenols is discussed.     

Cationic surfactant-selective potentiometric sensors based on neutral ion-pair carrier complexes

Poly(vinyl chloride) (PVC) membrane electrodes to determine monomer concentrations of tetradecyltrimethylammonium ion (TTA⁺) and hexadecylpyridinium ion (HPy⁺) based on neutral ion-pair carrier complexes of tetradecyltrimethylammonium dodecyl sulfate (TTA⁺-DS⁻) and hexadecylpyridinium dodecyl sulfate (HPy⁺-DS⁻), respectively, are reported here. The electrodes exhibit a Nernstian slope of 59 mV per decade for TTA⁺ and a sub-Nernstian slope of 34.5 mV per decade for HPy⁺ ions. The TTA⁺ ion-selective electrode (ISE) and the HPy⁺-ISE can determine the monomer units down to concentrations as low as 4.0×10⁻⁴M and 1.66×10⁻⁵ M, respectively. The effect of various additives, such as the anionic polyelectrolyte sodium dextran sulfate and macrocyclic β-cyclodextrin, on the surface activity exhibited by the cationic surfactants TTA⁺-DS⁻ and HPy⁺-DS⁻, in the presence of background concentrations of NaCl was also examined with surfactant-selective sensors. The Gibbs free energy of micelle formation (ΔG _m ) of both surfactants in the presence of various additives was calculated and found to be less favorable with respect to an increase in the amount of additives due to less availability of cationic surfactant monomer units. The ion-pair complexes TTA⁺-DS⁻ and HPy⁺-DS⁻ were found to behave as selective carrier compounds in PVC membranes in determining the concentration of monomer units of both TTA⁺ and HPy⁺, respectively. The proposed sensors worked well at a fairly acidic pH of 1–6.5 with response time of 60 s. The sensors responded well to the surfactant ions even in the presence of additives at lower concentration. The lifetime of the sensors is 3 mon.     

Electrodeposition of catalytically active nickel for the oxygen evolution reaction — effects of anionic composition

Nickel electrodes were prepared by electrodeposition in electrolytes of various anionic compositions. The deposition conditions and bath types were evaluated with special emphasis on the electrocatalytic properties for the oxygen evolution reaction (OER). Electrochemical characterizations in a 5 mol/L KOH solution at 25°C showed that the electrode deposited from the chloride bath, having a low Tafel slope of 50 mV/dec and an overpotential of 396 mV at 100 mA/cm², is the most catalytically active among electrodes prepared in electrolytes of various anionic compositions. The electrode activity for the OER is related to the real surface areas, which depend on the anion compositions in the deposition bath and the deposition conditions.     

Ni添加对Ti_(0.47)V_(0.28)Mn_(0.15)Cr_(0.1)储氢合金电化学性能的影响

通过X射线衍射谱(XRD)、气态吸放氢行为(PCT曲线)、电化学充放电性能、电化学阻抗谱(EIS),考察了Ni添加对Ti_(0.47)V_(0.28)Mn_(0.15)Cr_(0.1)储氢合金的电化学性能的影响。结果表明:Ti_(0.47)V_(0.28)Mn_(0.15)Cr_(0.1)的电化学活性很差,在碱液中几乎不能放电,添加Ni之后得到了明显改善。随着Ni含量的增加,Ti_(0.47)V_(0.28)Mn_(0.15)Cr_(0.1)Ni_x(x=0～0.25)合金电极的放电容量先增大后减小,在x=0.15时达到最大值310mA·h·g~(-1)。