Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.

An improved palladium-based DMFCs cathode catalyst

A novel carbon-supported palladium-rich Pd3Pt1/C catalyst prepared by a modified polyol process showed a better cell performance than Pt/C in direct methanol fuel cells, which may be attributed to palladium's inactivity to methanol electro-oxidation while exhibiting good performance to oxygen reduction reaction.

Multi-walled carbon nanotubes supported Pt-Fe cathodic catalyst for direct methanol fuel cell

Multi-walled carbon nanotubes supported Pt-Fe cathodic catalyst shows higher specific activity towards oxygen reduction reaction as compared to Pt/MWNTs when employed as cathodic catalyst in direct methanol fuel cell.

Electrocatalytic properties of Cu-Zr amorphous alloy towards the electrochemical hydrogenation of nitrobenzene

The Cu-Zr amorphous alloy was studied as an electrocatalyst towards the electrochemical hydrogenation of nitrobenzene. The electrocatalyst was activated by chemical etching in HF solution. Resulted changes in the morphology, chemical composition and crystalline structure of the electrocatalyst surface were characterised by scanning electron microscopy, X-ray diffraction and Auger electron spectroscopy. The electrocatalytic properties of the Cu-Zr amorphous alloy were assessed by voltammetric measurements. Due to the formation and aggregation of Zr residue modified Cu nanocrystals on the surface caused by the selective dissolution of Zr components in the chemical etching, the activated amorphous alloy is an effective electrocatalyst for the electrochemical reduction reaction of nitrobenzene with aniline as the main product. The positive shift of the peak potential and accompanying increase in the value of peak current in voltammograms with increasing Cu content and decreasing Zr content of the alloy surface in the chemical etching are indicative of improved electrocatalytic activity. (C) 2002 Elsevier Science B.V. All rights reserved.

A novel urchinlike gold/platinum hybrid nanocatalyst with controlled size

In this paper, we have explored a simple and new strategy to obtain quasimonodisperse Au/Pt hybrid nanoparticles (NPS) with urchinlike morphology and controlled size and Pt shell thickness. Through changing the molar ratios of Au to Pt, the Pt shell thickness of urchinlike Au/Pt hybrid NPs could be easily controlled; through changing the size of Au NPs (the size was easily controlled from similar to 3 to similar to 70 nm via simple heating of HAuCl4-citrate aqueous solution), the size of urchinlike Au/Pt hybrid NPs could be facilely dominated. It should be noted that heating the solution (100 degrees C) was very necessary for obtaining three-dimensional (3D) urchinlike nanostructures while H2PtCl6 was added to gold NPs aqueous solution in the presence of reductant (ascorbic acid). The electrocatalytic oxygen reduction reaction (ORR, a reaction greatly pursued by scientists in view of its important application in fuel cells) and the electron-transfer reaction between hexacyanoferrate(III) ions and thiosulfate ions of urchinlike Au/Pt hybrid NPs were investigated. It is found that the as-prepared urchinlike Au/Pt hybrid NPs exhibited higher catalytic activities than that of similar to Pt NPs with similar size.

Electrochemical chlorine sensor with multi-walled carbon nanotubes as electrocatalysts

It has been reported for the first time that an electrochemical gas sensor mdified with multi-walled carbon nanotubes (MWNTs) film as elctrocatalyst was fabricated for the determination of chlorine (Cl-2).Here, MWNTs and graphite were compared with each other in terms of their electrochemical properties using cyclic voltammetry. Cl-2 gas was allowed through the cathode surface of the sensor and the resulting galvanic effects were monitored. Results indicated that both of the MWNTs and graphite have the electrocatalytic activity for the reduction of Cl-2 while the MWNTs-modified electrode exhibited a higher accessible surface area in electrochemical reactions, excellent sensitivity, stable response, reproducibility and recovery for the determination of Cl-2.

Effect of borohydride as reducing agent on the structures and electrochemical properties of Pt/C catalyst

In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).

Preparation of divalent rare earth ions in air by aliovalent substitution and spectroscopic properties of Ln(2+)

When alkaline earth ions in borates, phosphates or borophosphates [SrB4O7, SrB6O10, BaB8O13, MBPO5 (M=Ca,Sr)] are substituted partially and aliovalently by trivalent rare earth ions such as Sm3+, Eu3+, these rare earth ions can be reduced to divalent state by the produced negative charge vacancy V-M". The matrices must have appropriate structure containing a rigid three-dimensional network of tetragonal AO(4) groups (A=B,P). These groups can surround and isolate the produced divalent RE2+ ions from the reaction with oxygen. Therefore, this reduction reaction can be carried out even in air at high temperature. The produced divalent rare earth ions can be detected by luminescence and XANES methods and their spectroscopic properties are discussed.

Chemiluminescence determination of trace ascorbic acid with chromium (VI)-H2O2-luminol system

A new chemiluminescence(CL) system for the determination of ascorbic acid has been established. By the fast reduction reaction between chromium(VI) and ascorbic acid, chromium(M was generated to react with luminol and hydrogen peroxide in alkaline aqueous solution and hydrogen peroxide to produce CL. The CL emission intensity was correlated with ascorbic acid concentration in the range 8.0 x 10(-9) to 1.6 x 10(-4) mol/L, and the detection limit was 8.0 x 10(-9) mol/L ascorbic acid. The relative standard deviation (n = 11) for 1.0 x 10(-6) mol/L ascorbic acid is 0.9%. The method has been applied to the determination of ascorbic acid in vitamin C tablets with satisfactory results.

Novel polyaryletherketones containing various pendant groups .1. Synthesis and characterization

Novel high glass transition temperature polyaryletherketones, containing pendant amido, alkyl, and carboxyl groups with reduced viscosity above 0.54 dL/g, were synthesized via solution nucleophilic polycondensation reaction of phenolphthalin, 2',2 ''-diisopropyl-5',5 ''-dimethylphenolphthalin, and 3,3'-bis(4-hydroxyphenyl)isobenzopyrrolidone with bis(4-nitrophenyl)ketone in the presence of potassium carbonate. By ion exchange with Na+ and K+, four ionomers were also prepared. A new monomer simultaneously containing carboxyl and algyl substituents was synthesized by reduction reaction of 2',2 ''-diisopropyl-5',5 ''-dimethyl-phenolphthalein. The resulting polymers were soluble in a few polar aprotic solvents; transparent, colorless, and tough films could easily be cast from DMF or DMSO solution. The mechanical properties of the films were excellent; and their tensile strength, elongation at break, and tensile moduli were in the range of 67.1-97.1 MPa, 7.8-165%, and 1.47-2.27 GPa, respectively. The prepared polymers showed fairly good thermal stability and resonably high glass transition temperatures above 210 degrees C. (C) 1997 John Wiley & Sons, Inc.

In situ external reflection FTIR spectroelectrochemical investigation of poly(o-phenylenediamine) film coated on a platinum electrode

The electrochemically deposited poly(o-phenylenediamine) film on a Pt electrode has been investigated utilizing in situ external reflection FTIR spectroelectrochemistry technique. The prepared ladder polymer film is found to be partially ring-opened. The dopant ClO4- is evidenced to orient in such a way that more than one oxygen atom attach to the charge sites of the polymer. This suggests that positive charges of oxidized polymer are partially delocalized over the whole chains. The proton movement observed during the oxidation reaction is associated with the solvated MeCN molecule. It is proposed that the proton diffusion, dissolvation and protonation of the film may be essential to the electrochemical reduction reaction of the film. Copyright (C) 1996 Elsevier Science Ltd.

氯离子和硫酸盐还原菌对Q235钢溶解氧还原反应的影响

在海水环境中，溶解氧阴极还原反应是钢铁材料腐蚀的主要因素之一，海水中的氯离子（Cl−）和硫酸盐还原菌（SRB）可能对溶解氧还原反应发生作用从而影响钢铁材料的腐蚀行为。本文以海洋工程材料Q235钢作为研究对象，通过循环伏安法、电化学阻抗谱、旋转圆盘电极和旋转圆盘-圆环电极线性扫描伏安法等电化学方法，研究了Cl−和硫酸盐还原菌对Q235钢电极表面溶解氧还原反应的影响，并对其影响机制进行了探讨。 研究表明：Q235钢在模拟混凝土孔隙液中电极表面氧化物的还原反应和溶解氧的还原反应同时进行；溶解氧还原反应在阴极反应电位范围内最初为混合过程控制的二电子反应，电位较负时为扩散过程控制的四电子反应。当在0.02 M Ca(OH)2溶液中加入Cl−时，随着Cl−浓度的增加，溶液电阻减小，溶解氧还原反应峰电位逐渐正移，即溶解氧还原反应的过电位减小；同时随着氯离子浓度的增加溶解氧还原反应速率逐渐减小。 由于硫酸盐还原菌在电极表面形成的生物膜阻碍了溶解氧到达电极表面，使得溶解氧还原反应与无菌时相比在一定程度上受到抑制，溶解氧还原反应速率降低；同时由于硫酸盐还原菌形成生物膜的作用，使得溶解氧还原机理也发生了改变，在没有硫酸盐还原菌时溶解氧还原以四电子还原为主，当硫酸盐还原菌数量较少时，溶解氧还原反应以二电子反应主，当硫酸盐还原菌数量较多时转为一电子反应为主。

Development of electrocatalysts for direct alcohol fuel cells

In the present review, we summarize the recent progress in electrocatalysts for direct alcohol fuel cells, focussing on the research of electrocatalysts for both alcohol oxidation and oxygen reduction, which are crucial in the development of fuel cells. A modified EG (ethylene polyol) method to prepare well-dispersed nano-sized Pt-based electrocatalysts with high loadings is reported. By this method, a more active carbon supported PtRu catalyst for methanol oxidation reaction and a PtSn catalyst for ethanol oxidation reaction have been synthesized successfully. Furthermore, a methanol tolerant Pd-based catalyst for cathode oxygen reduction reaction has been developed. HRTEM and HR-EDS have been employed to characterize the microstructure and micro-components of the above electrocatalysts. Results show that the bimetallic electrocatalysts prepared by the modified EG method display uniform size and homogeneous components at nanometer scale.

LPCVD of tungsten by selective deposition on silicon

Beta-phase W, selectively grown at 440C had resistivity 20 micro-ohm cm and maximum layer thickness 100nm. Hydrogen passivation proved essential in this process. Higher deposition temperatures resulted in increased layer thickness but incorporated WSi2 and alpha- phase W. Self limiting W grown on polycrystalline and heavily doped silicon yielded reduced thickness. Boron is involved in the WF6 reduction reaction but phosphorus is not and becomes incorporated in the W layer. The paper establishes an optimised and novel CVD process suited to IC contact technology. A funded technology transfer contract with National Semiconductor Greenock (M Fallon) resulted from this work.

A comprehensive aerosol spray method for the rapid photocatalytic grid area analysis of semiconductor photocatalyst thin films

Indicator inks, previously shown to be capable of rapidly assessing photocatalytic activity via a novel photo-reductive mechanism, were simply applied via an aerosol spray onto commercially available pieces of Activ (TM) self-cleaning glass. Ink layers could be applied with high evenness of spread, with as little deviation as 5% upon UV-visible spectroscopic assessment of 25 equally distributed positions over a 10 cm x 10 cm glass cut. The inks were comprised of either a resazurin (Rz) or dichloroindophenol (DCIP) redox dye with a glycerol sacrificial electron donor in an aqueous hydroxyethyl cellulose (HEC) polymer media. The photo-reduction reaction under UVA light of a single spot was monitored by UV-vis spectroscopy and digital images attained from a flat-bed scanner in tandem for both inks. The photo-reduction of Rz ink underwent a two-step kinetic process, whereby the blue redox dye was initially reduced to a pink intermediate resorufin (Rf) and subsequently reduced to a bleached form of the dye. In contrast, a simple one-step kinetic process was observed for the reduction of the light blue redox dye DCIP to its bleached intermediates. Changes in red-green-blue colour extracted from digital images of the inks were inversely proportional to the changes seen at corresponding wavelengths via UV-visible absorption spectroscopy and wholly indicative of the reaction kinetics. The photocatalytic activity areas of cuts of Activ (TM) glass, 10 cm x 10 cm in size, were assessed using both Rz and DCIP indicator inks evenly sprayed over the films: firstly using UVA lamp light to activate the underlying Activ (TM) film (1.75 mW cm(-2)) and secondly under solar conditions (2.06 +/- 0.14 mW cm(-2)). The photo-reduction reactions were monitored solely by flat-bed digital scanning. Red-green-blue values of a generated 14 x 14 grid (196 positions) that covered the entire area of each film image were extracted using a Custom-built program entitled RGB Extractor(C). A homogenous degradation over the 196 positions analysed for both Rz (Red colour deviation = 19% UVA, 8% Solar: Green colour deviation = 17% UVA, 12% Solar) and DCIP (Red colour deviation = 22% UVA, 16% Solar) inks was seen in both UVA and solar experiments, demonstrating the consistency of the self-cleaning titania layer on Activ (TM). The method presented provides a good solution for the high-throughput photocatalytic screening of a number of homogenous photocatalytically active materials simultaneously or numerous positions on a single film; both useful in assessing the homogeneity of a film or determining the best combination of reaction components to produce the optimum performance photocatalytic film. (C) 2010 Elsevier B.V. All rights reserved.