Synthesis of nanoscale antimony particles

For the search of new negative electrodes of Li-ion batteries, a low-temperature method has been developed for the preparation of nanoscale antimony particles which uses an alkoxide-activated sodium hydride as reducing agent of antimony pentachloride. X-ray diffraction and TEM studies confirm the obtaining of amorphous Sb nanoparticles dispersed in an organic matrix. ¹²¹Sb Mössbauer spectroscopy gives evidence for the occurrence of interactions between antimony and the matrix. These interactions are modified by the washing treatments.     

Synthesis of ZnS nanorods by annealing precursor ZnS nanoparticles in NaCl flux

ZnS nanorods were fabricated by annealing precursor ZnS nanoparticles, which were prepared by one-step, solid-state reaction of ZnCl₂ and Na₂S through grinding by hand at ambient temperature, in NaCl flux. The as-prepared ZnS nanorods have diameters of 40-80 nm, and lengths up to several micrometers. The structural features and chemical composition of the nanorods were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and Raman spectra.     

A pseudobinary approach to study interdiffusion and the Kirkendall effect in multicomponent systems

Interdiffusion studies become increasingly difficult to perform with the increasing number of elements in a system. It is rather easy to calculate the interdiffusion coefficients for all the compositions in the interdiffusion zone in a binary system. The intrinsic diffusion coefficients can be calculated for the composition of Kirkendall marker plane in a binary system. In a ternary system, however, the interdiffusion coefficients can only be calculated for the composition where composition profiles from two different diffusion couples intersect. Intrinsic diffusion coefficients are possible to calculate when the Kirkendall markers are also present at that composition, which is a condition that is generally difficult to satisfy. In a quaternary system, the composition profiles for three different diffusion couples must intersect at one particular composition to calculate the diffusion parameters, which is a condition that is almost impossible to satisfy. To avoid these complications in a multicomponent system, the average interdiffusion coefficients are calculated. I propose a method of calculating the intrinsic diffusion coefficients and the variation in the interdiffusion coefficients for multicomponent systems. This method can be used for a single diffusion couple in a multicomponent pseudobinary system. The compositions of the end members of a diffusion couple should be selected such that only two elements diffuse into the interdiffusion zone. A few hypothetical diffusion couples are considered in order to validate and explain our method. Various sources of error in the calculations are also discussed.     

Preparation of nanoscale organosols and hydrosols via the phase transfer route

Aqueous reactions support the preparation of a wide variety of inorganic nanoparticles (NPs), starting from relatively inexpensive precursors. However, the long-term stability of hydrosols is sensitive to changes in water chemistry, especially at high NP concentrations. On the other hand, by using an appropriate stabilizer, NPs prepared in organic phases more commonly display smaller sizes, higher stability, and monodispersity. Subsequently, phase transfer of freshly prepared NPs from an aqueous medium into an organic carrier constitutes a reliable and inexpensive route for preparing highly concentrated and stable organosols. The reverse transfer serves the preparation of small-sized and highly monodispersed hydrosols. The kinetics of phase transfer and the stability of the resultant sols are key considerations and are reliant on mixing and on the hydrophilic/lipophilic balance (HLB) of the particles. This balance is in turn dependent on the surface interaction between the phase transfer agent and the particles, as well as the interactions between the phase transfer agent, the continuous phase, and other additives, whenever applicable. This article reviews different studies that examined the phase transfer of NPs between organosols and hydrosols and elucidates the governing interactions. Scale-up of this preparation route lies in readily dispersible dried coated particles, or stable highly concentrated sols. Particle-independent multi-cycle phase transfer, with a minimum effect on NP size, monodispersity, and functionality is an attractive frontier.

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Observation of the spin-based plasmonic effect in nanoscale structures

Observation of surface-plasmon phenomena that are dependent upon the handedness of the circularly polarized incident light (spin) is presented. The polarization-dependent near-field intensity distribution obtained in our experiment is attributed to the presence of a geometric phase arising from the interaction of light with an anisotropic and inhomogeneous nanoscale structure. A near-field vortex surface mode with a spin-dependent topological charge was obtained in a plasmonic microcavity. The remarkable phenomenon of polarization-sensitive focusing in a plasmonic structure was also demonstrated.     

Charge transfer via interfaces, especially of nanoscale materials

Received: 27 March 1998     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Synthesis of nickel nanoparticles supported on hollow samaria-doped ceria particles via the solution-spray plasma technique: Anode catalysts for SOFCs

Aiming at SOFC anode applications, we have synthesized nanometer-sized nickel catalysts supported on hollow spherical particles of samaria-doped ceria (Ni/SDC) by spraying a mixed solution of nickel, samarium, and cerium nitrates into an atmospheric pressure plasma. The as-prepared particles consisted of SDC (average diameter d_SDC = ca. 0.8 µm) and uniformly dispersed nanometer-sized NiO particles. When reduced in H₂ at 800 °C or 1000 °C, Ni nanoparticles (average diameter d_Ni = 34 nm) were found to be embedded uniformly into the SDC surface.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Synthesis of hollow nanoparticles by plasma polymerization

A capacitively coupled low pressure plasma is used to produce particles by plasma polymerization of various organic precursors. The particles produced by this method are spherical, submicron in diameter, and contain a hollow center. Sixteen organic molecules were tested for the ability to produce hollow particles. Of these, 12 were found to reproducibly result in the formation of hollow particles while the other 4 either produced non-hollow particles or no particles at all under the conditions investigated here. Cyclohexane derivatives and the presence of an aromatic ring correlate strongly with a tendency to form hollow centers. The particle sizes vary from 70 nm to nearly 1 m and the core diameter is on the average 18 of the particle diameter. The corresponding shell thickness ranges from 24 nm for styrene to about 360 nm for cyclohexane. To explain the formation of hollow centers a mechanism is proposed based on the hypothesis that the solid phase is formed via crosslinking and solidification of viscous drop. This mechanism explains the observed linear relationship between core size and particle size.     

Microstructural stability of the Kirkendall plane in solid-state diffusion

In a diffusion-controlled interaction, the Kirkendall plane, as marked by inert particles placed at the original contact surface of a reaction couple, need not be unique. Multiple planes can develop, and sometimes the Kirkendall plane does not exist at all. A phenomenological approach is introduced to rationalize the Kirkendall-effect-mediated migration of macroscopic inclusions inside a diffusion zone.     

非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征, 建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知, 纳米簇是多孔的, 可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+, 在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散, 有利于快速阳离子交换, 其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明, 最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响, 结果表明, 微波辅助阳离子交换法信噪比较高, 操作简便, 可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系, 结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论: 所有这些特点, 使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200–600 °C temperature range, its cubic phase of 2–3 nm size, prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 °C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction, transmission electron microscopy, and UV–visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 °C annealed samples, under ultraviolet light excitation.     

非荧光硫化锌纳米簇的合成与表征

合成硫化锌纳米簇并对其进行表征,建立一种利用硫化锌纳米簇的阳离子交换(CX)反应检测痕量生物分子的方法。采用水热法合成非荧光硫化锌纳米簇(NCCs)并对其进行表征。纳米簇的性能直接影响检测结果。通过透射电镜图像和X射线衍射可知,纳米簇是多孔的,可以通过快速阳离子交换反应从纳米簇中释放大量的Zn2+,在锌响应试剂的作用下产生荧光信号进行荧光检测。其晶体的外部比内部排列松散,有利于快速阳离子交换,其晶体尺寸大小与加热时间有关。通过比表面积检测法测定纳米簇的表面积和孔径表明,最小的纳米簇拥有相对较大的表面积及较高的阳离子交换效率。实验了三种释放方法(酸溶解法、阳离子交换法和微波辅助阳离子交换法)对Zn2+释放性能的影响,结果表明,微波辅助阳离子交换法信噪比较高,操作简便,可用于硫化锌纳米簇免疫测定法中。比较了Zn2+的释放效率和目标结合力与平均直径之间的关系,结果表明纳米簇尺寸为44 nm时表现出最高的阳离子交换效率。结论：所有这些特点,使ZnS纳米簇阳离子交换放大器在痕量生物分子检测方面成为高度灵敏、生物相容性好、低廉环保的检测工具。     

Charge carriers responsible for the photo effect and photovoltaic effect in ZnS crystals

Contributions from thermalized and nonequilibrium, nonthermalized charge carriers to the photoeffect and the photovoltaic effect are considered.     

Synthesis of sea urchin-like LiMn2O4 hollow macrospheres via in situ conversion for rechargeable lithium-ion batteries

Among several materials (transition metal oxide) under development for use as a cathode in lithium-ion batteries, cubic spinel LiMn₂O₄ is one of the most promising cathode materials. In this study, the sea urchin-like LiMn₂O₄ hollow macrospheres were synthesized by using sea urchin-like α-MnO₂ precursors through solid-state in situ self-sacrificing conversion route. The as-prepared LiMn₂O₄ was assembled by many single-crystalline “thorns” of ca.10–20 nm in diameter and ca. 400–500 nm in length. Galvanostatic battery testing showed that sea urchin-like LiMn₂O₄ had an initial discharge capacity of 126.8 mAh/g at the rate of 0.2 C in the potential range between 3.0 and 4.5 V. More than 96.67 % of the initial discharge capacity was maintained for over 50 cycles. The improved electrochemical properties were attributed to the reduced particle size and enhanced electrical contacts by the materials. This particular sea urchin-like structured composite conceptually provides a new strategy for designing electrodes in energy storage applications.     

Simple preparation of hollow carbon sphere via templating method

The hollow carbon sphere (HCS) was synthesized using silica particle and sucrose as a template and carbon precursor, respectively, under a hydrothermal condition. The prepared HCS were characterized by SEM, TEM and N₂ adsorption. The prepared HCS showed uniforms size and high mesoporosity. It was found that the presence of acidic site on the silica particle templates would be crucial for the preparation of the HCS. Without the acidic site on silica particles, the macroporous carbon with high microporosity was prepared. It was found that the method employed in this work was highly suitable for the preparation of monodisperse HCS.     

Preparation of nanoscale MgFe2O4 via non-conventional mechanochemical route

The single-step synthesis of nanosized MgFe₂O₄ via mechanochemical processing of binary oxide precursors is reported. The mechanochemical route is followed by X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy. The nanoscale nature of the mechanosynthesized material is evidenced by transmission electron microscopy. Quantitative information is provided on both ionic and spin configurations in nanosized MgFe₂O₄.