Composition Of Metal Particles Research Articles

Effects of Composition and Size of Active Metal Particles on Electrochemical Performance and Characteristics of Sodium Metal Chloride Rechargeable Batteries

Because of the limitation of lithium resources, sodium-based rechargeable batteries started to emerge as potential candidates for medium and large-scale stationary energy storage system (ESS) again. Na-S batteries have been used for large-scale stationary ESS but intrinsically have a risk for explosion. Sodium metal chloride batteries based on Na-NiCl2 chemistry, however, are consisted of safer electrode configuration with nickel, NaCl and NaAlCl4 as cathode ingredients than the Na-S batteries. The Na-NiCl2 batteries offer many attractive properties such as high cell voltage, high theoretical specific energy, and broad range in operating temperature. The nickel chloride electrode plays an important role in the cell performance. A qualitative and quantitative understanding of the electrochemical and morphological properties of the active metals, therefore, is very important. This paper will describe effects of iron addition to cathode side as an active material and size of the active metal particles on electrochemical performance and characteristics of the sodium metal chloride batteries.

Pd–Cu interaction in Pd/Cu-MCM-41 catalysts: Effect of silica source and metal content

Pd/Cu-MCM-41 catalysts for the hydrodechlorination of CF3OCFClCF2Cl to CF3OCFCF2 were prepared. Palladium- and copper-containing samples (Pd/Cu=1 molar ratio) were synthesized by adding Pd2+ and Cu2+ during the formation of MCM-41, and then the slurries were aged by microwave-hydrothermal treatment. The effect of the silica source (silicates or TEOS) and total metal loading (2.4 and 4.0wt.%) on the chemical–physical properties and catalytic performances was studied. Bimetallic silicate-derived samples show features similar to those of the pristine MCM-41, regardless of the total metal content. Conversely, the long-range order of the mesoporous structure decreases for TEOS-derived catalysts, and large metal contents seem to alter the structure for these materials.During template removal by thermal treatment, palladium and copper are on the surface of MCM-41 particles, forming Pd1−xCuxO solid solutions whose composition is silica source-dependent. The amount of copper in Pd1−xCuxO is greater for TEOS-derived samples.After reduction, both Pd- and Cu-enriched alloys were found by XRD in silicate-derived samples, while XPS measurements indicated that the surface of the catalyst is enriched with copper. XRD and XPS analyses on TEOS samples indicated that the surface Cu/Pd ratio is closer to 1, and fcc PdCu alloys with a high copper content were identified. The composition of metallic particles modifies the selectivity, TEOS-derived catalysts being more selective to the target CF3OCFCF2.

Enhancement of electrical conductivity, dielectric anisotropy and director relaxation frequency in composites of gold nanoparticle and a weakly polar nematic liquid crystal

We report complex permittivity characteristics in composites of gold nanoparticles (GNP) and a weakly polar nematic liquid crystal possessing a low frequency director relaxation. Differential calorimetric measurements show that the inclusion of GNP has a strong influence on the isotropic–nematic (fluid–orientational fluid) transition temperature as well its first order character in terms of the transition entropy. The absolute value of conductivity increases by two to three orders of magnitude with respect to that for the host liquid crystal and its concentration dependence is demonstrated to be described by the percolation scaling law generally observed in composites of metal particles and polymers. However, the obtained exponent is much smaller, possibly owing to thermal fluctuations present in the fluid-like nematic medium. The activation energy governing the temperature dependence of conductivity is much higher in the nematic than in the isotropic phase. The frequency dependence of the ac conductivity exhibits a critical frequency that is concentration-dependent, but the exponents obtained defy Jonscher's Universal Response principle. A surprising feature is the observation of a substantial increase of not only the principal permittivity values, but their anisotropy as well. These studies also constitute the first report on the influence of GNP on the director relaxation mode of nematics. In contrast to the behaviour of the static permittivity, the dynamics of the system as measured using the director relaxation is seen to become faster with the presence of GNP. We provide an explanation for this antagonistic behaviour in terms of the alignment of the liquid crystal molecules in the vicinity of GNP, and the importance of the weak polarity of the liquid crystals used.

Metal Particle Emissions in the Exhaust Stream of Diesel Engines: An Electron Microscope Study

Scanning electron microscopy and transmission electron microscopy were applied to investigate the morphology, mode of occurrence and chemical composition of metal particles (diesel ash) in the exhaust stream of a small truck outfitted with a typical after-treatment system (a diesel oxidation catalyst (DOC) and a downstream diesel particulate filter (DPF)). Ash consists of Ca-Zn-P-Mg-S-Na-Al-K-phases (lube-oil related), Fe, Cr, Ni, Sn, Pb, Sn (engine wear), and Pd (DOC coating). Soot agglomerates of variable sizes (<0.5-5 μm) are abundant upstream of the DPF and are ash-free or contain notably little attached ash. Post-DPF soot agglomerates are very few, typically large (>1-5 μm, exceptionally 13 μm), rarely <0.5 μm, and contain abundant ash carried mostly from inside the DPF. The ash that reaches the atmosphere also occurs as separate aggregates ca. 0.2-2 μm in size consisting of sintered primary phases, ca. 20-400 nm large. Insoluble particles of these sizes may harm the respiratory and cardiovascular systems. The DPF probably promotes breakout of large soot agglomerates (mostly ash-bearing) by favoring sintering. Noble metals detached from the DOC coating may reach the ambient air. Finally, very few agglomerates of Fe-oxide nanoparticles form newly from engine wear and escape into the atmosphere.

Wear debris from hip prostheses characterized by electron imaging

Abstract The characterization of wear particles is of great importance in understanding the mechanisms of osteolysis. In this unique study, thirty-one tissue samples were retrieved at revision surgeries of hip implants and divided into four groups according to the composition of metal prosthetic components. Tissue samples were first analyzed histologically and then by scanning electron microscopy (SEM) combined with back-scattered electron imaging and energy dispersive X-ray spectroscopy. Therefore, particles were studied directly in situ in tissue sections, without the requirement for particle isolation. The composition of metal wear particles detected in the tissue sections corresponded to the composition of the implant components. A considerable number of large metal particles were actually clusters of submicron particles. The clustering of submicron particles was observed primarily with CoCrMo (cobalt-chromiummolybdenum) and, to a lesser extent, for stainless steel particles. SEM secondary and back-scattered electron imaging was an appropriate and selective method for recognizing the composition of metal particles in the in situ tissue sections, without destroying their spatial relationship within the histology. This method can be used as a screening tool for composition of metal and ceramic particles in tissue sections, or as an additional method for particle identification.

Synthesis and Stabilization of Supported Metal Catalysts by Atomic Layer Deposition

Supported metal nanoparticles are among the most important catalysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer-Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition-precipitation to control and tune these factors, to establish structure-performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leads to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe ALD oxide overcoats applied with atomically precise thickness control that stabilize metal catalysts while preserving their catalytic function. We also discuss strategies for generation and control over the porosity of the overcoats that allow the embedded metal particles to remain accessible by reactants, and the details for ALD alumina overcoats on metal catalysts. Moreover, using methanol decomposition and oxidative dehydrogenation of ethane as probe reactions, we demonstrate that selectively blocking low coordination metal sites by oxide overcoats can provide another strategy to enhance both the durability and selectivity of metal catalysts.

Vapour phase formic acid decomposition over PdAu/γ-Al2O3 catalysts: Effect of composition of metallic particles

A series of 1.8wt.% PdAu/γ-Al2O3 catalysts with a mean metal particle size of more than 10nm and different Pd/Au ratios were prepared by impregnation followed by hydrazine reduction and tested in the decomposition of vapour phase formic acid (2.2vol.%, 1bar) with and without added CO to the gas mixture. The catalytic activity was correlated with the bulk (AAS, XRD, EDS/TEM) and surface (XPS) composition of PdAu particles. A novel result was obtained that the surface composition of the particles did not change despite a considerable variation of the Au atomic fraction and it was found to be close to that of the Pd2Au alloy. The activity of the Au/Al2O3 catalyst was negligible compared with that of the Pd/Al2O3 catalyst being a factor of 65 lower per gram of metal at 403K. The surface electronic properties (XPS) and the catalytic activity of the Pd2Au layer calculated per one surface Pd atom (TOF) did not depend on the bulk composition of the metal particles. A lower activity of the Pd2Au layer as compared with the pure Pd layer (2–3 times) was observed, but the activation energies for the Pd and PdAu catalysts were similar (40kJmol−1) and were lower than that for the Au/Al2O3 catalyst (62kJmol−1). Addition of CO led to a considerable inhibition of the reaction for all PdAu catalysts, this being accompanied by an increase in the activation energy to 69kJmol−1.

Palladium–zinc catalysts on mesoporous titania prepared by colloid synthesis. II. Synthesis and characterization of PdZn/TiO2 coating on inner surface of fused silica capillary

Nanoparticle-doped mesoporous titania coating was synthesized by incorporation of PdZn nanoparticles into TiO2 sol followed by dip coating of the sol on inner surface of fused silica capillary. Monodispersed PdZn bimetallic colloidal particles with average particle diameters of approximately 2 nm have been prepared by an ethylene glycol reduction of ZnCl2 and Pd(CH3COO)2 in the presence of polyvinylpyrrolidone. The textural properties, surface structure, chemical composition, and morphology of the samples were investigated by means of N2 sorption measurements, TEM, and X-ray diffraction. PdZn/TiO2 coating has been further analyzed by quantitative analysis of the SAXS data in combination with the density contrast method, providing direct structural-dispersion information about the active component and support. Calcination conditions suitable for surfactant removal have been optimized to obtain PdZn/TiO2 coatings with required metal particle size and composition. The high dispersion and chemical composition of the nanoparticles embedded in mesoporous titania coating have been retained with no modification after thermal treatment in vacuum at 300 °C. Results suggest how porous structure of the PdZn coating may be fine-tuned to improve the accessibility of the pores to reactants. The control of the pore size in the range of 4.9–6.8 nm of the mesoporous titania was achieved by adding co-surfactants, such as n-butanol.

Synthesis and Treatment Parameters for Controlling Metal Particle Size and Composition in Cu/ZnO Materials—First Evidence of Cu3Zn Alloy Formation

This paper deals with the study of the conditions of obtention of small metal copper particles on ZnO using easy synthesis methods and activation treatments, which were found “efficient” for the preparation of copper particles on silica, that is, deposition–precipitation with urea and incipient wetness impregnation. For the latter, four different copper precursors were used: copper(II) nitrate, acetylacetonate, bis-ethylenediamine, and tetraamine. Activation treatments were performed under different gas reducing conditions (H2 or CO in N2), temperatures between 280 and 350 °C, and isotherm between 1 min and 2 h, with or without a precalcination step. Transmission electron microscopy (TEM), UV–visible spectroscopy, and X-ray diffraction (XRD) techniques were used to characterize the samples at the different stages of the synthesis route. The TEM results showed that it is not as easy as on silica to make small copper particles on ZnO. However, some experimental conditions were found to lead to particles around 4 nm: impregnation with copper acetylacetonate or copper bis-ethylenediamine, followed by calcination before reduction in H2. The important result of this work is that depending on the final temperature of reduction under hydrogen, it was possible to form either metal Cu particles (280 °C) or Cu3Zn alloy particles (350 °C); this was directly proved by XRD and indirectly by UV–visible spectroscopy. However, the formation of Cu3Zn could be avoided if the reducing gas H2 was replaced by CO in N2. To our knowledge, this is the first time that the formation of Cu3Zn alloy particles is evidenced in Cu/ZnO samples.

Sub-Micrometer Particles Produced by a Low-Powered AC Electric Arc in Liquids

The article presents the report of the production of composites of sub-micrometer metal particles in matrix consisted of the metal compounds by means of an AC electric arc in water and paraffin solutions using electrodes carbon-metal and metal-metal (metal: Ni, Fe, Co, Cu). The advantage of this method is the low electric power (from 5 to 10 W) needed in comparison to standard DC arc-discharge methods (0.8 to 3 kW). This method enables the production of particles from conductive material also in wide range of temperature and in solvent which could be either transparent to light or opaque. Moreover the solvent can be electrolyte or insulating liquid. The microstructure of the composite layer was investigated by scanning electron microscopy (SEM), Electron Probe Microanalysis (EPMA) and X-ray. During particles production in water metal oxides were created. Additionally using cobalt-copper, nickel-copper as couple electrodes, insoluble in water copper (II) hydroxide crystal grains were created additionally which crystals shape was depended on transition metal. For iron-copper couple electrodes system the copper (II) hydroxide was not formed. Experiments with sequence production of Ni and Fe particles with C electrode assisting in molten paraffin let to obtain both Ni and Fe particles surrounded by paraffin. After solidification the material was insulator but if locally magnetic field influenced on the liquid solution in that place after solidification a new composite was created which was electric current conductor with resistivity around 0.1 omega x m, was attracted by magnetic field and presented magneto resistance around 0.4% in changing magnetic field in a range 150 mT. After mixing the concentrated paraffin with normal paraffin resistivity of the mixture increased and it became photosensitive and created small voltage under light influence.

Tailoring the synthesis of supported Pd catalysts towards desired structure and size of metal particles

In a systematic study, the influence of different preparation parameters on phase composition and size of metal crystallites and particles in Pd-Cu/TiO(2) and Pd-Sb/TiO(2) catalyst materials has been explored. Temperature and atmosphere of thermal pretreatment (pure He or 10% H(2)/He), nature of metal precursors (chlorides, nitrates or acetates) as well as of ammonium additives (ammonium sulfate, nitrate, carbonate) and urea were varied with the aim of tailoring the synthesis procedure for the preferential formation of metal particles with similar size and structure as observed recently in active catalysts after long-term equilibration under catalytic reaction conditions in acetoxylation of toluene to benzylacetate. Among the metal precursors and additives, the chloride metal precursors and (NH(4))(2)SO(4) were most suitable. Upon thermal pretreatment of Pd-Sb or Pd-Cu precursors, chloroamine complexes of Pd and Cu are formed, which decompose above 220 degrees C to metallic phases independent of the atmosphere. In He, metallic Pd particles were formed with both the co-components. In H(2)/He flow, Pd-Cu precursors were converted to core-shell particles with a Cu shell and a Pd core, while Sb(1)Pd(1) and Sb(7)Pd(20) alloy phases were formed in the presence of Sb. Metal crystallites of about 40 nm agglomerate to particles of up to 150 nm in He and to even larger size in H(2)/He.

Dielectric relaxation of glass particles with conductive nano-coatings

This research focuses on the dielectric properties of particles consisting of glass cores with nanometre conductive coatings. The effects of the core glass particle shape (sphere, flake and fibre) and size are investigated for different coating characteristics over the frequency range 0.5–18 GHz. Experimental results for the coated glass particle combinations show the existence of a dielectric loss peak. This feature is associated with interfacial relaxation between the insulating core glass particle and the nanoscale conductive coating. The relaxation mechanism provides enhanced loss that is not observed in conventional solid metal particle composites. The results are fitted to a model, which shows that the relaxation frequency increases with increasing coating conductivity and thickness, with additional parameters identified for further particle optimizations.

The hydrogenation of triglycerides using supported alloy catalysts. II. Silica-supported Pd-Cu catalysts

Silica-supported Ni-Ag catalysts with a loading of 2·1·0.6% (w/w) total metal have been prepared using the precursors nickel dimethylglyoxime and silver nitrate by means of a simple impregnation method. The resulting catalysts were activated by calcination at 260°C in air, followed by hydrogen reduction at 450°C. They were then employed for soyabean oil hydrogenation at 1 bar H2 pressure and 160°C in a stirred batch reactor. Characterisation of the catalysts using temperature-programmed reduction and electron microscopy indicated that alloying of nickel and silver had occurred, but metal particle composition, for a given overall composition, varied with metal particle size and smaller metal particles were nickel rich. The hydrogenation activity and selectivity measurements revealed that the catalysts were more active and selective than a commercial nickel catalyst. Furthermore, the specific activities of the alloy catalysts were a maximum for alloys in the range 70–90 at. % Ni. However, the supported alloy catalysts also gave rise to greater trans isomerisation than the commercial catalyst. This is attributed to hydrogen deficiency caused by large triglyceride molecules blocking hydrogen chemisorption on small nickel particles (10–50 A in diameter), leading to enhanced cis-trans isomerisation.

Glucose sensors made of novel carbon nanotube‐gold nanoparticle composites

Carbon nanotube and metal particle composites have been exploited to fabricate high performance electrochemical devices. However, the physical and chemical procedures to synthesize the composites are labor intensive and inefficient. Our study reveals an one-step wet chemistry method to accomplish fast and controllable production of gold nanoparticle (AuNP) and carbon naotube (CNT) composites. Such a process is sensitive to the surface charge. Especially, when functionalized with carboxyl groups, the CNTs carried negative charges and showed low level association with negatively charged AuNPs. Thermal treatment was employed to decompose the carboxyl groups and render each CNT a charge-free surface thereby achieving a high level AuNP-CNT association. The fabricated glucose sensors demonstrated dependence of their sensitivities to the amount of AuNPs on the CNTs. The enhancement of sensitivity can be attributed to an accelerated electron transfer rate from glucose oxidase Gox to the electrode. The Michaelis-Menten kinetics also indicated improved performance in the glucose sensor made of AuNP-CNTs. Therefore, our research revealed a novel approach to produce metallic nanoparticle and CNT composite for fabricating high performance electrochemical sensors.

PtRu Nanoparticle Electrocatalyst with Bulk Alloy Properties Prepared through a Sonochemical Method

Properties of PtRu nanoparticles prepared using high-intensity sonochemistry are reported. Syntheses were carried out in tetrahydrofuran (THF) containing Ru3+ and Pt4+ in a fixed mole ratio of either 1:10 or 1:1. X-ray diffraction measurements confirmed sonocation produces an alloy phase and showed that the composition of the nanometer scale metal particles is close to the mole fraction of Ru3+ and Pt4+ in solution with deviations that tend toward Ru enrichment in the alloy phase. The materials gave responses that are similar in terms of peak potential and current density, referenced to the catalyst active surface area, to those of bulk alloys in voltammetry experiments involving CO stripping and CH3OH electrochemical oxidation in 0.1 M H2SO4. The results show that sonochemical methods have the potential to produce nanometer scale bimetallic electrocatalysts that possess alloy properties. The materials have application in mechanistic studies of fuel cell reactions and as platforms for the development of CO tolerant fuel cell catalyst.

Ternary alloy nanoparticles with controllable sizes and composition and electrocatalytic activity

The ability to tailor the size and composition of metal particles at the nanoscale could lead to improved or new catalytic properties. This paper reports the results of an investigation of the preparation and the characterization of platinum–nickel–iron (PtNiFe) ternary alloy nanoparticles. The synthesis of monolayer-capped ternary PtNiFe nanoparticles involved controlling the ratios of metal precursors, capping agents, and reducing agents in a single organic phase. The average diameters of the resulting nanocrystalline cores were well controlled between 1.4 and 1.8 nm with high monodispersity (±0.2–0.4 nm). The catalysts were prepared by loading the as-synthesized PtNiFe nanoparticles onto a high surface area carbon support and subsequent thermal treatment optimized for achieving effective shell removal and alloy formation, as well as controllable size, composition and metal loading. The catalysts were characterized using TEM, DCP-AES, FTIR, TGA, and XRD techniques. The catalysts were also examined for their intrinsic kinetic activities for the electrochemical oxygen reduction reaction. It is shown that the ternary catalysts are highly active towards molecular oxygen electrocatalytic reduction. Implications of our findings for the exploration of the new nanostructured catalyst materials for applications in fuel cell catalysis are also discussed.

Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles

In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0–14.3 wt.%. This constant reached a maximum between 14.3 and 21.4 wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles.

Fabricating gold nanoparticle–oxide nanotube composite materials by a self-assembly method

Composition of nanostructured metal particles on oxide tubes (TiO 2 and ZrO 2) were fabricated and characterized. The composite materials were examined by transmission electron microscopy, scanning electron microscopy, FT-IR absorption, and UV–visible absorption spectra. The results of characterization showed that the composites indeed contained both oxide tubes and gold nanoparticles and that the gold nanoparticles were intimately associated with the nanotubes.

Characterization of heavy metal particles embedded in tire dust

Tire dust is a significant pollutant, especially as a source of zinc in the urban environment. This study characterizes the morphology and chemical composition of heavy metal particles embedded in tire dust and traffic-related materials (brake dust, yellow paint, and tire tread) as measured by a field emission scanning electron microscope equipped with an energy dispersive X-ray spectrometer (FESEM/EDX). In 60 samples of tire dust, we detected 2288 heavy metal particles, which we classified into four groups using cluster analysis according to the following typical elements: cluster 1: Fe, cluster 2: Cr/Pb, cluster 3: multiple elements (Ti, Cr, Fe, Cu, Zn, Sr, Y, Zr, Sn, Sb, Ba, La, Ce, Pb), cluster 4: ZnO. According to their morphologies and chemical compositions, the possible sources of each cluster were as follows: (1) brake dust (particles rich in Fe and with trace Cu, Sb, and Ba), (2) yellow paint (CrPbO 4 particles), (3) brake dust (particulate Ti, Fe, Cu, Sb, Zr, and Ba) and heavy minerals (Y, Zr, La, and Ce), (4) tire tread (zinc oxide). When the chemical composition of tire dust was compared to that of tire tread, the tire dust was found to have greater concentrations of heavy metal elements as well as mineral or asphalt pavement material characterized by Al, Si, and Ca. We conclude that tire dust consists not only of the debris from tire wear but also of assimilated heavy metal particles emitted from road traffic materials such as brake lining and road paint.

Effect of Support on the Size and Composition of Highly Dispersed Pt–Sn Particles

Platinum and tin deposited on γ-Al 2O 3, MgO, and Mg(Al)O supports were investigated by CO chemisorption and analytical electron microscopy in the scanning transmission electron microscopy with energy-dispersive X-ray spectrometry (STEM/EDX). Composition and size of individual particles in the 1-nm range are presented and results are compared with dispersion measurements obtained from volumetric chemisorption. We demonstrate that dispersion determined by chemisorption measurements can give unrealistically low values, possibly caused by metal–support interaction, while STEM/EDX reveals the correct size of metal particles. The metal–support interaction seems not to be present on γ-Al 2O 3 support but only on Mg(Al)O and MgO supports. The performance of the catalyst in propane dehydrogenation is related to the amount of Pt on the metal particle surface. It is shown that there is a relationship between the composition of metal particles and the activity of the catalyst. The most active is a catalyst that contains metal particles with high Pt content; however, some Sn is necessary for reduced coking and probably for increased stability.