纳米核壳式铜-锡双金属粉的制备及性能研究

A kind of novel core-shell Cu-Sn bimetallic nanoparticles has been prepared by a new method (displacement method), in which Sn was made to cover on the surface of Cu nano-core. The preparation method and reaction mechanism have been discussed. This reaction happened under the existence of coordinate agent-(NH₂)₂CS and protective agent PVP. The nanoparticles prepared were with a core-shell structure, granule diameter between 50～100 nm and good dispersing capability. The Cu-Sn nanoparticles proposed has better oxidation-resistant ability than Cu nanoparticles with corresponding granule diameter and can be applied as lubricant additives as well as antibacterial agent. When the additive amount is very low (0.1wt‰～0.5wt‰), it can improve the P_B of the lubricant by 92%～106%, and also enhance its antiwear characteristics and friction-reducing properties. At the concentration of 1 000 ppm, it can reach an antibacterial ratio of 99.99%.     

Photoinduced Electron Transfer between CdS and CdTe Nanoparticles in Colloidal Solutions

The photochemical behavior of solutions containing a mixture of CdS and CdTe nanoparticles under pulsed irradiation conditions was investigated. It was shown that electron transfer from the CdS particles to the CdTe nanoparticles occurs during the photoexcitation of such systems. The effectiveness of the process is increased with increase in the size of the CdTe nanoparticles. Such behavior is due to decrease in the potential of the CdTe conduction band with increase in the size of the nanoparticles as a result of the appearance of quantum-dimensional effects.     

聚丙烯/纳米蒙脱土复合材料的结晶动力学研究

采用热分析方法，研究了聚丙烯／纳米蒙脱土复合材料（PP／CLAY）的等温结晶行为，并分别用Avrami方程和赵志英方法对所得数据进行了分析，研究结果表明，纳米蒙脱土微粒对聚丙烯等温和非等温结晶行为均有不同程度的影响，可提高聚丙烯的结晶速率并改善结晶结构。     

Ultrafine molybdenum carbide nanoparticles supported on nitrogen doped carbon nanosheets for hydrogen evolution reaction

Nitrogen doped carbon nanosheets supported molybdenum carbides nanoparticles (Mo_xC/NCS) have been synthesized by tuning the mass ratio of melamine and ammonia molybdate. The Mo₂C/NCS-10 exhibits superior electrocatalytic performance and stability for HER, which was attributed to N-doped carbon nanosheets, small particle size, mesoporous structure, and large electrochemical active surface area.     

Conventional and unconventional infrared spectrometry and their quantitative interpretation

In condensed matter, optical properties can be described by a dielectric function (DF), and the structures observed in spectra are then related to the poles and zeros of the DF. As an example, model functions are calculated by a fit to measured spectroscopic data for polystyrene and silica. The first material shows weak, narrow bands and the latter strong, broad bands and a negative real part of the DF.Based on these model DFs, spectra are simulated which are expected to be obtained by “conventional” methods such as transmittance or reflectance measurements, or by “unconventional” methods such as reflectance at oblique incidence, diffuse reflectance, photoacoustic spectroscopy and attenuated total reflectance. A variety of simulated, typical spectra are plotted as a small “atlas”. Conditions are discussed that allow a straightforward procedure for interpreting the spectra quantitatively, i.e., the evaluation of the resonance frequency and the concentration of the oscillators under consideration.It is shown that for systems characterized by weak, narrow oscillator lines, mostly an intuitive interpretation is possible, looking only at the position and strength of “lines” in the spectra. Materials showing strong polar vibrations, however, require more sophisticated procedures for interpreting the spectra.     

Computer Simulation of the Structure of Porous Electrodes with an Immobilized Enzyme and Nanosized Support Particles

The efficiency of the operation of a porous electrode with an immobilized enzyme is defined, in particular, by a lucky structure of its active layer, which can contain nanosized particles of the support. The composites of such a kind are prepared with the aid of methods of colloidal chemistry. The aim of this particular investigation is to perform a computer simulation of processes of coagulation of particles of the support and their possible heterocoagulation with molecules of the enzyme. Algorithms of the formation of nanocomposite structures in solution are suggested. Calculations show that the concentration of the enzyme molecules in the nanocomposite structures cannot exceed a certain critical value. On the other hand, at a fixed value of the concentration of the enzyme molecules, the concentration of the support particles must not fall below a certain threshold quantity, which provides for the passing of current through the active layer. In order for all the enzyme molecules, rather than for a fraction of these, in the composite to take part in the process of bioelectrocatalysis, the concentration of support particles must be increased even higher, to an optimum value.__________Translated from Elektrokhimiya, Vol. 41, No. 6, 2005, pp. 738–747.Original Russian Text Copyright © 2005 by Chirkov, Rostokin.     

Poly(ethyleneimine) as reducing and stabilizing agent for the formation of gold nanoparticles in w/o microemulsions

This paper is focused on the use of branched poly(ethyleneimine) (PEI) as reducing as well as stabilizing agent for the formation of gold nanoparticles in different media. The process of nanoparticle formation was investigated, in the absence of any other reducing agents, in microemulsion template phase in comparison to the nucleation process in aqueous polymer solution.

On the one hand, it was shown that the polyelectrolyte can be used for the controlled single-step synthesis and stabilization of gold nanoparticles via a nucleation reaction and particles with an average diameter of 7.1 nm can be produced.

On the other hand, it was demonstrated that the polymer can also act as reducing and stabilizing agent in much more complex systems, i.e. in water-in-oil (w/o) microemulsion droplets. The reverse microemulsion droplets of the quaternary system sodium dodecylsulfate (SDS)/toluene–pentanol (1:1)/water were successfully used for the synthesis of gold nanoparticles. The polymer, incorporated in the droplets, exhibits reducing properties, adsorbs on the surface of the nanoparticles and prevents their aggregation. Consequently, nanoparticles of 8.6 nm can be redispersed after solvent evaporation without a change of their size.

Nevertheless, the polymer acts already as a “template” during the formation of the nanoparticles in water and in microemulsion, so that an additional template effect of the microemulsion is not observed.

The particle formation for both methods is checked by means of UV–vis spectroscopy and the particle size and size distribution are investigated via dynamic light scattering and transmission electron microscopy (TEM).     

Hydrogenation of nitrobenzenes catalyzed by platinum nanoparticle core-polyaryl ether trisacetic acid ammonium chloride dendrimer shell nanocomposite

Platinum nanoparticle core-polyaryl ether trisacetic acid ammonium chloride dendrimer shell nanocomposites (Pt@G_n-NACl) were prepared and used as catalysts for hydrogenation of nitrobenzenes to anilines with molecular hydrogen under mild conditions. The as-prepared nanoparticles have mean particle size from 2.0 to 5.5 nm, depending on the molar ratio of the metal and the dendrimer. The Pt nanoparticles demonstrate near-monodisperse when the molar ratio of Pt and G₃-NACl is below 30. The interaction among three carboxyl groups terminated at the dendron and the metallic core keeps the Pt nanoparticles from agglomerating. The colloidal solution of Pt nanoparticles stabilized by the dendrimer, in which the molar ratio of Pt/G₃-NACl was less than 60, is stable without precipitation for several weeks. The dendrons attach to the metal core radially, and a substantial fraction of the surface of the metal nanoparticle is unpassivated and available for catalytic reactions. Turnover frequencies for the hydrogenation of nitrobenzenes to anilines change from 353 to 49 h⁻¹ depending on the dendrimer generation and substrates. The dendrimer catalysts are stable during the catalytic hydrogenation process and can be recovered by centrifugation and reused. The results suggest the effectiveness of polyaryl ether trisacetic acid ammonium chloride dendrimer as a stabilizer for the preparation of Pt nanoparticle catalysts.     

Amperometric glucose biosensor based on electrodeposition of platinum nanoparticles onto covalently immobilized carbon nanotube electrode

A new amperometric biosensor for glucose was developed based on adsorption of glucose oxidase (GOx) at the gold and platinum nanoparticles-modified carbon nanotube (CNT) electrode. CNTs were covalently immobilized on gold electrode via carbodiimide chemistry by forming amide linkages between carboxylic acid groups on the CNTs and amine residues of cysteamine self-assembled monolayer (SAM). The fabricated GOx/Au_nano/Pt_nano/CNT electrode was covered with a thin layer of Nafion to avoid the loss of GOx in determination and to improve the anti-interferent ability. The immobilization of CNTs on the gold electrode was characterized by quartz crystal microbalance technique. The morphologies of the CNT/gold and Pt_nano/CNT/gold electrodes have been investigated by scanning electron microscopy (SEM), and the electrochemical performance of the gold, CNT/gold, Pt_nano/gold and Pt_nano/CNT/gold electrodes has also been studied by amperometric method. In addition, effects of electrodeposition time of Pt nanoparticles, pH value, applied potential and electroactive interferents on the amperometric response of the sensor were discussed.

The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for glucose in the absence of a mediator. The linear range was from 0.5 to 17.5 mM with correction coefficient of 0.996. The biosensor had good reproducibility and stability for the determination of glucose.     

Solvent and thiourea adsorption/intercalation effects on the solid-state electrochemistry of α-phase nickel hydroxide nanoparticles

Nanoparticles of α-phase nickel hydroxide were synthesized by a single-step hydrothermal method using urea as the hydrolytic agent. Precipitated powders were of pure turbostratic α-phase as confirmed by x-ray diffraction profile. The ageing of α-Ni(OH)₂ in 1.0 M alkali solutions is investigated for pure non-intercalated α-Ni(OH)₂ and thiourea intercalated/absorbed α-phase nanomaterials. The α-Ni(OH)₂ powder immobilized on the surface of graphite electrodes shows a gradual α→β phase transformation with continuous voltammetric cycling, and the concentration gradient of water that exists in the layered-double-hydroxide-like interlayers of α-phase and the solution was shown to play a crucial role on the high electrochemical activity of this phase nickel hydroxide. To understand the role of water in the ageing process, concomitant entries of non-aqueous solvents like ethanol and acetonitrile along with thiourea were effected. Cyclic voltammetric measurements of thiourea-treated α-Ni(OH)₂ samples revealed that hydroxyl ion influx during the anodic oxidation depends on the counter flux of solvent molecules, and if the intercalated the solvent is acetonitrile, then the electrochemical activity of α-Ni(OH)₂ reduced drastically; Q _a/Q _c>1 for water as solvent in the interlayers α-Ni(OH)₂ and Q _a/Q _c<1 for ethanol and acetonitrile as solvents. The α-phase gets stabilized in the presence of thiourea with water and ethanol as co-intercalates. Transmission electron microscope images of α-Ni(OH)₂ and thiourea-treated samples show a change in particle size and morphology. Elemental CHNS analysis confirms the presence of sulphur in the thiourea intercalated samples.