Chemical vapor generation atomic spectrometry using amineboranes and cyanotrihydroborate(III) reagents

Amineboranes of the type L-BH3 (L = NH3; tert-BuNH2; Me2NH; Me3N) and sodium cyanotrihydroborate(III) (NaBH3CN) have been tested as derivatization reagents in the generation of volatile hydrides and elemental mercury following aqueous phase reaction with ionic species of Hg(II), As(III), As(V), Sb(V), Sb(III), Bi(III), Se(IV), Se(VI), Te(IV), and Te(VI). Continuous flow generation atomic absorption spectrometry coupled with a flameless quartz tube atomizer (T = 25 degrees C) and a miniature argon-hydrogen diffusion flame atomizer were employed for the detection of mercury vapors and volatile hydrides, respectively. All of the reductants were able to reduce Hg(II) to the elemental state, giving sensitivities comparable to NaBH4 reduction. Under reaction conditions giving maximum sensitivity for hydride generation with NaBH4, only some amineboranes are able to produce volatile hydrides from all the elements. No evidence of hydride formation was observed from the Se(VI) and Te(VI). In general, the reducing power decreased in the order NaBH4 > H3N-BH3 > tert-BuNH2-BH3 > NaBH3CN > or = Me2HN-BH3 > Me3N-BH3. In comparison with THB, amineboranes and NaBH3CN allowed, in general, a better control of interference effects of Fe(III), Ni(II), Co(II), and Cu(II). Application to determination of mercury in certified reference material is reported. The most likely mechanism of reaction of borane complexes in chemical vapor generation is based on the direct action of hydrogen bound to boron.     

Octithiophene on Cu(III) and Au(III): formation and electronic structure of molecular chains and films

Adsorption and electronic structure of octithiophene (8T) molecules on Cu(III) and Au(III) surfaces are investigated using scanning tunneling microscopy (STM) and spectroscopy (STS) at room temperature. We find a large difference in adsorption behavior of 8T molecules on the two surfaces. At the initial stage of adsorption, 8T molecules are stabilized in the form of molecular chain on a terrace of Cu(III), whereas neither such chain structure nor isolated 8T molecules have been observed on a terrace of Au(III). By increasing the amount of adsorbed molecules, a disordered monolayer film is formed on Cu(III) while a well-ordered monolayer film is formed on Au(III). From the spectroscopic investigations using bias-dependent STM images and STS spectra and by comparing the data with theoretical calculations, it is found that the electronic property of 8T molecules in the molecular chain on Cu(III) is different from that of a free-standing 8T molecule while that in the monolayer film on Au(III) keeps original character of the free-standing 8T molecule. The present study shows that adsorption of 8T molecules on Cu(III) results in a formation of adsorption-induced states near the Fermi level.     

Magnetic and Morphological Properties of Electrodeposited Thick FePt Films on Metallic (Au, Ag, Cu) Underlayers

Electrodeposited thick films of FePt (with the nominal composition 50 % Fe/50 % Pt) on three metallic (Au, Ag, Au) underlayers were annealed at various temperatures. The magnetic and morphological properties of the resulting films were then monitored. The Au and Ag underlayers promoted the growth of the (bct) L1₀ FePt phase. The greater growth of this phase in the films deposited on the Ag underlayer led to the crystallographic texturing in the (001) direction. This was accompanied by a significant magnetic anisotropy and a negative shift of the remanent magnetization in the presence of an applied field. The coercivity of the Ag underlayer films increased to 18 kOe while the coercivity of the Au underlayer films decreased to ～2 kOe when the annealing temperature was increased to 800 ^°C.     

Solid-state synthesis of amorphous iron(III) phosphate at room temperature and its absorption properties for Hg(II) and Ag(I) ions

Amorphous iron(III) phosphate has been synthesized by solid-state reaction at room temperature and was characterized by several methods. The non-crystalline sample displayed the particle size within the range of 100-200 nm, and it had a strong fluorescence emission peak centered at 306.6 nm. Moreover, its absorption properties for Hg(II) and Ag(I) heavy metal ions have been investigated. The experimental research results revealed that its excellent absorption capacity for Hg(II) and Ag(I) could reach to 1.831 mmol/g and 1.354 mmol/g, respectively, at pH = 5.98 and the absorption time t = 6 h. The absorption properties for Hg(II) were usually stronger that those for Ag(I).     

Preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions in environmental samples by membrane filtration prior to their flame atomic absorption spectrometric determinations

A method for separation-preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions by membrane filtration has been described. The method based on the collection of analyte metal ions on a cellulose nitrate membrane filter and determination of analytes by flame atomic absorption spectrometry (FAAS). The method was optimized for several parameters including of pH, matrix effects and sample volume. The recoveries of analytes were generally in the range of 93-100%. The detection limits by 3 sigma for analyte ions were 0.02microgL(-1) for Pb(II), 0.3microgL(-1) for Cr(III), 3.1microgL(-1) for Cu(II), 7.8microgL(-1) for Ni(II) and 0.9microgL(-1) for Cd(II). The proposed method was applied to the determination of lead, chromium, copper, nickel and cadmium in tap waters and RM 8704 Buffalo River Sediment standard reference material with satisfactory results. The relative standard deviations of the determinations were below 10%.     

Bi(III)4-methylpiperidinedithiocarbamate coprecipitation procedure for separation--pre-concentration of trace metal ions in water samples by flame atomic absorption spectrometric determination

A pre-concentration method was developed for determination of trace amounts of cadmium, copper and lead in water samples by FAAS after coprecipitation by using potassium 4-methylpiperidinedithiocarbamate (K4-MPDC) as a chelating agent and Bi(III) as a carrier element. This procedure is based on filtration of the solution containing precipitate on a cellulose nitrate membrane filter following Cd(II), Cu(II) and Pb(II) coprecipitation with Bi(III)4-MPDC and then the precipitates together with membrane filter were dissolved in concentrated nitric acid. The metal contents of the final solution were determined by FAAS. Several parameters including pH of sample solution, amount of carrier element and reagent, standing time, sample volume for precipitation and the effects of diverse ions were examined. The accuracy of the method was tested with standard reference material (MBH, C31XB20 and CRM BCR-32) and Cd, Cu and Pb added samples. Determination of Cd, Cu and Pb was carried out in sea water, river water and tap water samples. The recoveries were >95%. The relative standard deviations of determination were less than 10%.     

Growth of Ag, Au, Cu, and Pt nanostructures on surfaces by micropatterned laser-image formations

Silver, gold, copper and platinum nanoparticles (NPs) were grown on surfaces in the form of patterns by the exposure of laser radiation onto droplets of metal ion solutions and the aid of a reducing agent. The generation of patterns from metallic NPs was achieved by combining induced growth of NPs and nanostructures by laser incidence directly on surfaces and optical image formation techniques for transferring the patterns. Near-UV (363.8 nm) and visible (532 nm) laser wavelengths were used for the laser-induced growth of NPs into microstructures on glass, quartz, stainless steel, silicon, and gold-on-silicon substrates. The sizes of the patterns formed were on the micrometer scale and the sizes of the transferred patterns were on the millimeter scale. The patterns formed were generated by optical transference of image and interference of laser beams. Ag and Au substrates were highly active in surface enhanced Raman spectroscopy (SERS). The enhanced Raman activity was measured for SERS probe molecules: 9H-purin-6-amine (adenine) and 1,2-bis (4-pyridyl)-ethane analytes on Ag and Au substrates, respectively. The enhancement factors obtained were 1.8×10(5) and 6.2×10(6), respectively.     

Complex oxide structures formed by oxidation of Ag(100) and Ag(111) by hyperthermal atomic oxygen

Abstract

Silver (100) and (111) single crystals were exposed to a unique hyperthermal atomic oxygen source, which produces a high flux of 5.1eV atomic oxygen, for seven hours at 220°C. The resultant oxide and oxide–metal interfaces were characterized by optical, scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HREM). The oxide scale was more than 10 µm thick and very weakly attached to the Ag substrate. The silver oxides were complex and surprising, differ in their thickness and the oxide phases due to the orientation of the Ag single crystals. The cross-section TEM studies revealed complex microstructures with many defects, such as micro-twins, porosity and irregular shaped grains.     

AAS法连续测定钯合金中的Au,Cu,Pt,Zn

介绍了AAS法快速测定多元贵金属合金中Au,Cu,Pt,Zn的方法.结果表明,该法具有快速、准确的优点,应用于PdAgAuCuPtZn(35-30-10-14-10-1)合金的Au,Cu,Pt,Zn含量的测定,取得了满意的结果.     

Hg(0) oxidative absorption by K(2)S(2)O(8) solution catalyzed by Ag(+) and Cu(2+)

The aqueous phase oxidation of gaseous elemental mercury (Hg(0)) by potassium persulfate (K(2)S(2)O(8), KPS) catalyzed by Ag(+) and Cu(2+) was investigated using a glass bubble column reactor. Concentrations of gaseous Hg(0) and aqueous Hg(2+) were measured by cold vapor generation atomic absorption spectrometry (CVAAS). The effects of several experimental parameters on the oxidation were studied; these include different types of catalysts, pHs and concentrations of potassium persulfate, temperatures, Hg(0) inlet concentrations and tertiary butanol (TBA). The results showed that the removal efficiency of Hg(0) increased with increasing concentration of potassium persulfate and catalysts Ag(+), Cu(2+) and Ag(+) provided better catalytic effect than Cu(2+). For example, in the presence of 5.0mmoll(-1) KPS, the mercury removal efficiency could reach 75.4 and 97.0% for an Ag(+) concentration of 0.1 and 0.3mmoll(-1), respectively, and 69.8 and 81.9% for 0.1 and 0.3mmoll(-1) Cu(2+). On the other hand, high temperature and the introduction of TBA negatively affect the oxidation. Furthermore, the removal efficiency of Hg(0) was much greater in neutral solution than in either acidic or alkaline solution. But the influence of pH was almost eliminated upon the addition of Ag(+) and Cu(2+), and high Hg(0) inlet concentration also has positive impact on the removal efficiency of Hg(0). The possible catalytic oxidation mechanism of gaseous mercury by KPS was also proposed.     

Chemically induced permanent magnetism in Au, Ag, and Cu nanoparticles: localization of the magnetism by element selective techniques

We report a direct observation of the intrinsic magnetization behavior of Au in thiol-capped gold nanoparticles with permanent magnetism at room temperature. Two element specific techniques have been used for this purpose: X-ray magnetic circular dichroism on the L edges of the Au and 197Au M?ssbauer spectroscopy. Besides, we show that silver and copper nanoparticles synthesized by the same chemical procedure also present room-temperature permanent magnetism. The observed permanent magnetism at room temperature in Ag and Cu dodecanethiol-capped nanoparticles proves that the physical mechanisms associated to this magnetization process can be extended to more elements, opening the way to new and still not-discovered applications and to new possibilities to research basic questions of magnetism.     

Eutectoid decomposition in Fe2Si5 based alloys with a small amount of 10(Pd, Pt) and 11(Cu, Ag, Au) group elements

The addition of a small amount of Cu is effective in accelerating the + Si eutectoid decomposition. Some elements (Pd, Pt, Ag and Au) that are expected to have similar chemical properties were added to an Fe₂Si₅ based alloys up to 1.0 at.% to examine whether a similar effect could be revealed. The microstructures, X-ray diffraction and differential thermal analysis (DTA) of slowly solidified or heat treated specimens were investigated in detail. The solubility of all containing elements into the phase was less than 0.2 at.% for the slowly solidified specimen. The excess of the additive solidified as a phase of a eutectic with the Si phase. On the other hand, the solubility of these additives in the phase was classified into two groups. The first group had higher solubility in the phase than that in the phase. The solubility of the other group was as low as that in the phase. Pd and Au belonged to the former and Pt and Ag belonged to the later. The acceleration of the eutectoid decomposition was only observed in the former group but it was negligible in the later group. The existence of the eutectic melt at the annealing temperature was effective on the coarsening of the eutectoid structure but not essential for the acceleration. The eutectoid decomposition strongly depended on the solubility of these elements into the phase.     

Speciation determination of chromium(III) and (VI) using preconcentration cloud point extraction with flame atomic absorption spectrometry (FAAS)

bis-[2-Hydroxy-1-naphthaldehyde] thiourea was synthesized and preconcentration cloud point extraction (CPE) for speciation determination of chromium(III) and (VI) in various environmental samples with flame atomic absorption spectrometry (FAAS) has been developed. Chromium(III) complexes with bis-[2-hydroxynaphthaldehyde] thiourea is subsequently entrapped in the surfactant micelles. After complexation of chromium(III) with reagent, the analyte was quantitatively extracted to the surfactant-rich phase in the non-ionic surfactant Triton X-100 after centrifugation. The effect of pH, concentration of chelating agent, surfactant, equilibration temperature and time on CPE was studied. The relative standard deviation was 2.13% and the limits of detection were around 0.18 μg L⁻¹.     

A simple approach for facile synthesis of Ag,anisotropic Au and bimetallic (Ag/Au) nanoparticles using cruciferous vegetable extracts

We present a simple and straightforward approach for the synthesis and stabilization of relatively monodisperse Ag, Au and bimetallic (Ag/Au) nanoparticles by using cruciferous vegetable (green/red) extracts by simply adjusting the pH environment in the aqueous medium. The vegetable extracts act both as reducing and capping agents. The monometallic and bimetallic nanoparticles of Ag and Au so obtained were characterized by UV–visible spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM). It is shown that red cabbage extract can be used for the preparation of anisotropic Au nanoparticles. The formation of Au anisotropic nanoparticles was found to depend on a number of environmental factors, such as the pH of the reaction medium, reaction time, and initial reactant concentrations. Additionally, it is shown that these extract-stabilized Au and Ag nanoparticles can be used as a seed for preparation of bimetallic Au/Ag nanoparticles. For bimetallic alloy nanoparticles the absorption peak was observed between the two maxima of the corresponding metallic particles. The surface plasmon absorption maxima for bimetallic nanoparticles changed linearly with increasing Au mole ratio content in various alloy compositions. It has been shown that the formation of hollow Au spheres depends on the experimental conditions.     

Mechanism of generation of volatile hydrides of trace elements by aqueous tetrahydroborate(III). Mass spectrometric studies on reaction products and intermediates

The mechanism of generation of volatile metal/metalloid hydrides by derivatization with borane complexes is presented. This reaction has been employed for ultratrace element analysis since 1972 and has been the source of much controversy in regard to the reaction mechanism. Here we investigated this derivatization by using As(III), Sb(III), Bi(III), MeAsO(OH)2, and Me2AsO(OH) as model analytes and NaBH4, NaBD4, tert-BuNH2BH3, and Me2NHBH3 as borane reagents. The identification of reaction products and intermediates observed under various reaction conditions was performed by gas chromatography/mass spectrometry and electrospray ionization mass spectrometry. An alternative reaction model, based on the formation of analyte-borane complex (ABC) intermediates, is able to reconcile all the experimental evidence reported in the literature. In this study, we provide definitive evidence of the ABC hydride generation mechanism, which shows that the generation of volatile hydrides occurs via formation of ABC intermediates between hydroboron species and the analyte substrate followed by the direct transfer of hydrogen from boron to the analyte atom, and fast hydrolysis leading to the final product.     

（S,Au）与（S＋Au）增感的模式设计

本文主要论述了硫金增感依次分开加入[以下简称(S,Au)]与混合在一起后加入[以下简称(S Au)]的照相性能的差异,并从建立的模型来说明存在差别的原因.     

Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)

A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L(-1) HNO3 in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 microg L(-1). The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.