First-principles investigations of the Ni3Sn alloy at steam reforming conditions

The structure and surface composition of a Ni₃Sn alloy at conditions relevant for the steam reforming reaction was investigated using density functional theory calculations. Both the flat Ni₃Sn(0 0 0 1) surface and a surface with steps in the closed packed direction [1 0  0]were considered. The adsorption geometries and energies of the species CO, C, OH and H were calculated. Chemical potentials were used to map out which adsorbates are on the surface under varying conditions. It was found that adsorbates preferably bind to Ni as nearest neighbor with Sn as second-nearest neighbor. The binding energy is slightly stronger than on pure Ni. Adsorbate binding to Sn was found to be very unfavorable. Binding free energies indicate that at high temperature the alloy surface will be predominantly covered by CO and C, and at low temperatures one may find H and almost no OH. Even though the nominal composition of the investigated alloy is Ni₃Sn, the surface composition may differ significantly depending on temperature and pressure of the gas phase. This effect was investigated by calculating segregation energies both in the absence and in the presence of adsorbates. For the flat surface, it was found that only the bulk termination is present under relevant conditions. In contrast, it was found that for steps preferential adsorption of CO and C on Ni sites may lead to adsorption-induced segregation at temperatures below 400 °C. When taking segregation into account, the most stable Ni₃Sn surfaces will not bind CO or C at the same condition that Ni does. This is in excellent agreement with the previously proven ability of Ni-Sn alloys to inhibit graphite formation.     

Self-assembly of 5-octadecyloxyisophthalic acid and its coadsorption with terephthalic acid

The structure of the self-assembled monolayer of pure 5-octadecyloxyisophthalic acid (5OIA), and the coadsorption monolayer of 5OIA and terephthalic acid, is investigated using scanning tunneling microscopy (STM) at the liquid-solid interface. 5OIA self-assembles into a monolayer comprised of different structures. For the major phase, 5OIA molecules alternately pack with opposite enantiotopic faces in a lamella, giving lamellae with a chain-to-trough angle of ∼88°. Two adjacent lamellae are assembled together by a hydrogen-bonding network between two carboxylic acid groups from each lamella. In the self-assembled monolayer of the mixture solution of 5OIA and terephthalic acid, 5OIA molecules coadsorb with terephthalic acid and therefore form two stoichiometric multi-component domains. Each domain has a molar ratio of 2:1 for 5OIA and terephthalic acid. For each component (5OIA or terephthalic acid), the two coadsorption structures exhibit opposite chirality.     

铋膜电极溶出伏安法测定苍耳子中锌的含量

采用电位溶出法,用铋膜电极替代汞膜电极对中药苍耳子中微量元素锌的测定作了研究,考察了同位镀铋膜及测定微量元素锌的条件。实验结果表明：锌在以KSCN为支持电解质的铋膜电极上可得到灵敏的电位溶出峰,线性方程为：为I=2.0062C＋0.0069,相关系数为r=0.9967,检出限为6.0×10-8g/L线性范围为0.5×10-6—2.8×10-6mol/L,RSD=2.24%。该法简单快速,准确度和精密度均符合要求,回收率为89.5%—100.3%。     

离子液体[BDMIM]PF6修饰碳糊电极的制备及其电化学性能

以离子液体1,2-二甲基-3-丁基咪唑六氟磷酸盐（[BDMIM]PF6）代替传统液态石蜡为粘合剂与石墨粉相混合,制备了一种新型的离子液体修饰碳糊电极（IL/CPE）。采用扫描电子显微镜分别对其表面形貌和石蜡碳糊电极（CPE）表面形貌进行了表征。以亚铁氰化钾为电化学探针对IL/CPE的电化学行为进行了研究,并与CPE进行了比较。结果表明,[BDMIM]PF6由于具有较高的导电性,使IL/CPE比CPE具有更高的导电效率,铁氰化钾在电极上的可逆性变好,ΔEP值变小,峰电流响应增加10倍,电极过程由CPE上的吸附控制变为扩散控制,根据计时库仑法求解出铁氰化钾的扩散系数为5.52×10^-6cm2/s（25℃）。电化学交流阻抗图亦表明与不导电的液态石蜡油相比,离子液体的存在加快了电子传递。     

The spatial distribution of thermal and epithermal neutrons in a graphite moderated spallation neutron field

The Gamma-3 assembly is located at the Joint Institute for Nuclear Research, Dubna, Russia. It consists of a cylindrical lead target (ø = 8 cm, L = 58.8 cm) surrounded by reactor grade graphite (110 × 110 × 60 cm). The target was irradiated with a beam of 1.6 GeV deuterons from the Nuclotron accelerator and CR-39 track detectors coupled to LR-115 2B film were used to measure the slow neutron distribution on the surface of the graphite. The detection efficiency of the CR-39 in the CR-39/LR-115 2B system was measured using a custom made calibration setup and found to be (1.12 ± 0.05) × 10⁻³ and (6.1 ± 1.2) × 10⁻⁴ tracks per neutron, for thermal and epithermal neutrons respectively, under the etching and counting procedures described in this work. The irradiation of the Gamma-3 was also simulated using MCNPX 2.7 Monte Carlo code and good agreement between the experimental and calculated track densities was found. This serves as a good validation for the computational models used to simulate spallation neutron production, transport and moderation.     

Hillock formation on ion-irradiated graphite surfaces

Abstract

Scanning probe microscopy experiments show that ion irradiation of (0001) graphite results in the formation of isolated defects comprising of a few tens of atoms. We use molecular dynamics simulations and density-functional theory calculations to study the formation probabilities of these defects. We identify different defect structures which correspond to experimentally observed hillocks on graphite surfaces. We find that the predominant source of defects are vacancies and interlayer interstitials, and identify a three-atom carbon ring defect on the graphite surface.     

Analytical Scheme for the Direct Graphite-Atomizer/Flame Atomic Absorption Spectrometric Determination of Fifteen Trace Elements in Toenails for Biological Monitoring

An analytical scheme for the determination of up to fifteen trace elements in nails and hair has been proposed. Samples were solubilized by means of aqueous tetraalkylammonium hydroxide (alkyl = methyl or ethyl). Cadmium, Cr, Cu, Fe, Mn, Pb and Zn were determined by pulse-nebulization flame AAS, employing the Slotted Tube Atom Trap (STAT) for Cd and Pb. Suitable chemical modifiers have been applied in electrothermal AAS (ETAAS) determinations of Cd and Pb (ammonium hydrogen phosphate), As, Sb, Se and Sn (palladium), while no modifier was needed in determinations of Al, Co, Cr, Mn, Mo and Ni. Calibration was performed by means of matrix-matched standards and the technique was verified by standard additions, comparison with neutron activation and analysis of hair reference material. The usefulness of this technique for occupational exposure monitoring is briefly discussed.     

Practical Study into Enhancing IgG Immobilisation on Screen-Printed Electrodes for Environmental Applications

This work is focused on the influence of pH and applied potential for the immobilisation of rabbit IgG on a carbon screen-printed electrode. The orientation of IgG molecule at the surface is fundamental for activity and reproducibility of the immunosensor. As the electrode potential is increased a particular order may be brought to the immobilised antibodies, i.e. the antibodies adapt a more favourable arrangement on the surface to facilitate better binding. The response increased when changing the pH from basic to acidic medium and the reverse trend was observed for the limit of detection (LOD). When a potential was applied to the electrode, the response generally decreased and the LOD increased in the order acidic > basic > neutral pH. The LODs obtained from antibodies immobilised at acidic pH and + 100 mV were better than the LODs obtained at other conditions.     

Copper ring-disk microelectrodes: fabrication, characterization, and application as an amperometric detector for capillary columns

A novel approach to the fabrication of metal ring-disk (RD) microelectrodes is presented that employs flexible chemical vapor deposition (CVD) and electrode modification techniques. Specifically, the development of a copper ring-disk microelectrode is described utilizing a combination of CVD coating, electroetching, and electroplating. Initially, a 25 μm diameter tungsten wire is concentrically coated by CVD with an insulating layer of silica, a layer of tungsten metal, and finally, a second outer layer of silica. The copper surface was prepared by first creating micrometer cavities by electrochemical etching the tungsten in hydroxide solutions followed by electrodeposition of copper from aqueous solutions of Cu(II). Each step of the process was characterized by scanning electron microscopy, optical microscopy, and cyclic voltammetry, demonstrating the preparation of a viable metal-based dual ring-disk microelectrode system. For the purpose of demonstrating the concept of introducing specific selectivity into the device, amperometric detection of galactose in 0.1 M NaOH was performed at +0.60 V in bulk solution and after flow injection analysis in a capillary column.     

Determination of lead, copper and manganese by graphite furnace atomic absorption spectrometry after separation/concentration using a water-soluble polymer

In this study, a water-soluble polymer, polyvinylpyrrolidinone (PVP) having chelating functionalities was used for the preconcentration and separation of traces of Pb, Cu, Ve and Mn prior to their determination by graphite furnace atomic absorption spectrometry. For this purpose, the sample and the PVP solutions were mixed and the metal bound polymer was precipitated by adding the mixture onto acetone. The precipitate was separated by decantation and dissolved with water. By increasing the ratio of the volumes of sample to water used in dissolving the precipitate, the analyte elements were concentrated as needed. The concentration of trace elements was determined using graphite furnace atomic absorption spectrometry. The analyte elements in matrix free aqueous solutions were quantitatively recovered. The validity of the proposed method was checked with a standard reference material (NIST SRM 1577b bovine liver) and spiked fruit juice, sea water and mineral water samples. The analytical results were found to be in good agreement with certified and added values. Detection limits (3δ) were 1.7, 3.6 and 4.1 μg l⁻¹ for Pb, Cu and Mn, respectively, using 10 μl of sample volume. The method is novel and can be characterized by rapidity, simplicity, quantitative recovery and high reproducibility.