Determination of gold in geological samples at parts per milliard levels by flameless atomic-absorption spectroscopy

Summary A method is described for the determination of gold at ppM levels in geological materials by the use of flameless A. A. spectroscopy. The gold is separated as bromoaurate from HBr solution by methyl isobutyl ketone (MIBK). The MIBK phase is pipetted directly into an HGA-2000 Graphite Furnace. Detection limits of about 0.6–0.8 ppM Au for a 1-g sample are achieved. The error of determination (relative standard deviation) varies in the range 5–50%, depending on the absolute gold level.

---

Zusammenfassung Ein Verfahren zur Bestimmung von ppM-Mengen Gold in geologischem Material mit Hilfe der flammenlosen Atomarabsorption wurde beschrieben. Dabei wird das Gold als Bromoaurat aus bromwasserstoffsaurer Lösung mit Methylisobutylketon extrahiert. Die organische Phase wird unmittelbar in einen HGA-2000 Graphitofen pipettiert. Die Nachweisgrenze beträgt etwa 0,6–0,8 ppM Au in einer 1-g-Einwaage. Die relative Standardabweichung variiert je nach der absoluten Goldmenge zwischen 5 und 50%.

     

Determination of Hg(II) in acidic media by stripping voltammetry with collection

Stripping voltammetry with collection at a rotating ring-disk electrode having a platinum ring and a glassy-carbon disk was used for the determination of Hg(II) in 1.0M H(2)SO(4) medium in the range 0.10-4.00 ppM. Satisfactory results were obtained only after a thin film of Au (two monolayer equivalents) was electroplated on the disk electrode. The average relative deviation of the results for determination at the 0.10-ppM level was 7.5 %. The limit of detection for the technique is approximately 0.01 ppM.     

水洗处理对Au/TiO2催化剂光催化活性的影响

以Au(S2O3)3-2为金前驱体, 分别采用水洗(W)和旋蒸(E)工艺制备了Au/TiO2催化剂. 用UV-Vis漫反射光谱(DRS)、X 射线衍射(XRD)、透射电子显微镜(TEM)和原子吸收光谱(AAS)对制备的催化剂样品进行了表征, 通过光催化降解甲基橙对催化剂光催化活性进行了评价. 结果表明, 通过水洗处理, 催化剂样品表面形成了具有较好分散性的金纳米粒子(2-5 nm), 而旋蒸工艺制备的样品表面形成一层金的包覆结构. Au/TiO2催化剂的光催化活性与制备工艺密切相关. 在相似的金负载量下, 水洗法制备的样品比旋蒸法制备的样品具有更高的光催化活性.     

CO oxidation on Aun/TiO2 catalysts produced by size-selected cluster deposition

Planar model catalysts were prepared by deposition of size-selected gold clusters containing up to seven atoms on rutile TiO2 (110). Molecular oxygen is observed to bind inefficiently to the surface, probably at oxygen vacancies, and some oxygen also appears to bind to the gold clusters. Stable CO binding is observed atop gold for catalysts prepared by Au and Au2 deposition, but not for larger Aun. CO oxidation activity is strongly dependent on cluster size, with Au7-prepared samples >50 times more reactive than samples prepared by Au or Au2 deposition     

Rapid determination of gold in Romanian auriferous alluvial sands, concentrates and rocks by 14 MeV NAA

The nuclear and spectral interferences in the 14 MeV neutron activation analysis (NAA) of gold from Romanian auriferous alluvial sands, concentrates and rocks have been studied and the optimum of activation, cooling and measuring times was determined for a maximum peak-to-background ratio for gold. The contribution of the nuclear interfering elements in the samples, Hg and Pt, to the concentration of gold has been calculated and, concluded that the nuclear reactions ¹⁹⁷Au(n,2n)¹⁹⁶Au, ¹⁹⁷Au(n,2n)^196mAu and ¹⁹⁷Au(n,n')^197mAu can be used for gold determination, with minimal errors. Using the nuclear reactions ¹⁹⁷Au(n,n')^197mAu and ¹⁹⁷Au(n,2n)¹⁹⁶Au the spectral interferences are minimal and are due to Rb, Ti and V for a short irradiation and to Se for a long one. Two methods of fast gold determination were proposed for auriferous alluvial sands and rocks in the range of 20-2500 ppm, under the optimum conditions established so that the systematic errors of analysis due to the gold accompanying elements can be considerably diminished. For measuring the induced gamma-radioactivity in the samples either a short irradiation (25 seconds) with a NaI(Tl) detector or a long irradiation (3000 seconds) with a Ge(Li) detector were used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nondestructive analysis of the gold quarter liras

In this study, we have prepared seven Au-Cu standards in the concentration range of 18–24 (as carat) for nondestructive control of gold quarter liras. Some calibration curves for quantitative analysis of Au in the gold quarter liras that commercially present in Turkey have been plotted using these standard samples. The characteristic X-rays of Au and Cu emitted from these standard samples and the test sample with known composition are recorded by using a Ge(Li) detector. These calibration curves provide a nondestructive analysis of gold quarter liras with the uncertainties about 1.18%.     

Determination and distribution of gold in Greek bauxites of the Parnassos-Ghiona area by gamma-spectroscopy after ion exchange separation

For the determination of gold in Greek bauxites from the Parnassos-Ghiona area, an analytical technique was used based on the selective adsorption of gold on SRAFION NMRR chelating anion exchanger resin, after leaching the bauxites with aqua regia in a teflon-autoclave at 120 °C, and the determination of the retained gold directly on the resin by instrumental neutron activation analysis (INAA), using the 411.8 keV line of the ¹⁹⁸Au isotope. The procedure allowed to determine Au in concentrations down to ng/g. The obtained data were used to examine the distribution of Au in the profiles of a group of different bauxites from the upper or the called third bauxitic horizon of the Parnassos-Ghiona area in Greece. Especially in the basement of some bauxite deposits unexpected high concentrations of Au up to 2 mg/g have been found. Furthermore, the correlation of Au with other trace elements, found in the bauxitic samples, was investigated.     

SnO2负载Au和M-Au(M=Pt,Pd)催化剂及其低温催化氧化CO性能

以SnO₂为载体, 采用沉积沉淀法(DP)、共沉淀法(CP)和浸渍法(IM)制备了金负载Au/SnO₂催化剂, 同时采用沉积沉淀法制备了M-Au/SnO₂(M=Pd, Pt)双金属负载催化剂. 通过X射线衍射(XRD)、BET比表面积测定、透射电镜(TEM)和X射线光电子能谱(XPS)等技术对样品进行表征, 并测定其对CO的催化活性. 结果表明: 与CP法和IM 法相比, DP法制备的Au/SnO₂-DP 催化剂, Au 颗粒(<5 nm)较小, 分布均匀; Au/SnO₂-DP 中的Au 是以金属态Au0存在, 而Au/SnO₂-CP 和Au/SnO₂-IM 中, 金以Au⁰和Au³⁺的混合价态存在, 在Au/SnO₂-DP和M-Au/SnO₂中的Au、Pt、Pd和SnO₂之间存在相互作用; Au/SnO₂-DP 催化性能明显优于Au/SnO₂-CP 和Au/SnO₂-IM. Au与Pt 和Pd的双金属复合催化剂催化活性明显提高. 不同方法制备Au/SnO₂催化活性的差别主要是由于Au颗粒大小和Au氧化态的不同而产生. 而M-Au/SnO₂活性提高, 可能是由于Au与Pt 和Pd之间的相互作用.     

Glutathione-protected gold clusters revisited: bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals

Small gold clusters (approximately 1 nm) protected by molecules of a tripeptide, glutathione (GSH), were prepared by reductive decomposition of Au(I)-SG polymers at a low temperature and separated into a number of fractions by polyacrylamide gel electrophoresis (PAGE). Chemical compositions of the fractionated clusters determined previously by electrospray ionization (ESI) mass spectrometry (Negishi, Y. et al. J.Am. Chem. Soc. 2004, 126, 6518) were reassessed by taking advantage of freshly prepared samples, higher mass resolution, and more accurate mass calibration; the nine smallest components are reassigned to Au10(SG)10, Au15(SG)13, Au18(SG)14, Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, and Au39(SG)24. These assignments were further confirmed by measuring the mass spectra of the isolated Au:S(h-G) clusters, where h-GSH is a homoglutathione. It is proposed that a series of the isolated Au:SG clusters corresponds to kinetically trapped intermediates of the growing Au cores. The relative abundance of the isolated clusters was correlated well with the thermodynamic stabilities against unimolecular decomposition. The electronic structures of the isolated Au:SG clusters were probed by X-ray photoelectron spectroscopy (XPS) and optical spectroscopy. The Au(4f) XPS spectra illustrate substantial electron donation from the gold cores to the GS ligands in the Au:SG clusters. The optical absorption and photoluminescence spectra indicate that the electronic structures of the Au:SG clusters are well quantized; embryos of the sp band of the bulk gold evolve remarkably depending on the number of the gold atoms and GS ligands. The comparison of these spectral data with those of sodium Au(I) thiomalate and 1.8 nm Au:SG nanocrystals (NCs) reveals that the subnanometer-sized Au clusters thiolated constitute a distinct class of binary system which lies between the Au(I)-thiolate complexes and thiolate-protected Au NCs.     

Determination of trace metals in water using x-ray fluorescence spectrometry

A simple, rapid and accurate method for water analysis is proposed. The analytical procedure for the determination of Fe, Mn, Zn, Cu, Cd, As, Pb and Se in water in concentrations as low as a few ppM involves precipitation with a carrier of the metals by diethyldithiocarbamate (DDTC) or 1-(2-pyridylazo)-2-naphthol (PAN) and filitration through a Millipore filter. The precipitates collected on the filter disc are examined by X-ray fluorescence analysis. PAN is excellent for the determination of several metal ions at the ppM level, and DDTC can be used with tartrate as a masking agent if water samples contain large amounts of iron(III).     

Comparative studies of gold catalysts prepared via solvated metal atom impregnation and conventional impregnation: characterization and low-temperature co oxidation

Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (CI). X-ray photoelectron spectroscopy investigations indicated that gold in all the samples was in the metallic state. TEM and XRD measurements showed that the mean diameter of Au particles prepared by SMAI was smaller than that of those prepared by CI with the same gold content. Catalytic tests showed that SMAI catalysts had higher CO oxidation activity than CI catalysts with the same compositions. Both SMAI and CI Au/TiO₂catalysts exhibited high activities in low temperature CO oxidation. Full CO conversion was obtained at 323 K for 3.1 wt.% Au/TiO₂ (SMAI) catalyst, which displayed higher activity than the 3.1 wt.% Au/D-72(SMAI) and 3.1 wt.% Au/TiO₂(CI). Although the sizes of gold particles prepared by the same method and supported on both TiO₂ and resin were comparable, the Au/TiO₂ catalysts showed significantly higher activities than the Au/resin catalysts with the same Au contents under the same reaction conditions. These results prove that not only the gold particle size, but also the support plays a key role in CO oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Potentiometric titration of gold in ores with potassium iodide

Summary A direct potentiometric titration method for the determination of gold in ores and alloys is described. It is based on the reduction of Au(III) with iodide ions yielding accurate and reproducible results. Detection limit and sensitivity were 0.06 and 0.032 mg/l Au, respectively. The linear response range was between 0.1 and 120 mg/l Au. The method can be used for the routine assay of gold in different kind of samples.     

Au/SnO2的制备及其低温CO氧化催化性能

用沉积-沉淀法制备了不同金含量的Au/SnO2催化剂.采用XRD和UV-Vis等手段对催化剂样品进行了表征并考察了沉积溶液的pH值、金的负载量、焙烧温度和气氛等对Au/SnO2催化CO氧化活性的影响.结果表明：当沉积溶液的pH=9～10时,所制得的金属金的平均粒径最小；随着金的负载量的增大,金属金的粒径增大, Au/SnO2的催化活性降低；在所研究的条件下, Au/SnO2前驱体在空气中473 K下焙烧4 h,得到的催化剂活性最高；在氢气中373 K下处理2 h的Au/SnO2的催化活性在所有样品中是最高的.     

纳米Au/TS-1催化剂的制备及用于甲醇羰基化体系

采用负压沉积沉淀法、等体积浸渍法、负压等体积浸渍法等方法制备了纳米Au/TS-1催化剂,研究了深床焙烧和等离子体焙烧,以及焙烧温度和焙烧气氛对催化剂中纳米金粒子大小和催化性能的影响,并采用ICP、TEM、XRD、UV-vis、XPS对催化剂金粒子进行了物化性能表征,采用甲醇羰基化制乙酸甲酯反应表征催化性能.结果表明,不同制备方法、不同焙烧方法、不同焙烧温度和焙烧气氛对负载型纳米Au/TS-1沸石分子筛催化剂中金粒子的大小、形貌、物化性质和催化性能有明显影响.其中,3种制备方法中,氢气气氛下焙烧均比空气和氮气气氛下焙烧得到的催化剂的金粒子尺寸更小,分散更均匀,约为5~10 nm.与其它方法相比,负压沉积沉淀法可制得分散更均匀的金粒子,Au/TS-1沸石催化剂中的金粒子尺寸更小,平均粒径为1~5 nm.催化性能评价结果显示,3种方法制备出的负载型金催化剂用于催化甲醇羰基化制乙酸甲酯反应体系中,甲醇的转化率分别为85%、75%、60%,乙酸甲酯选择性可高达68%,反应温度200℃为最好.     

Preparation and characterization of gold nanoparticles and nanowires loaded into rod-shaped silica by a one-step procedure

Rod-shaped mesoporous silica nanoparticles (RMSN) with built-in gold nanoparticles or thin gold nanowires in the pore channels were in situ synthesized via a one-step procedure. The insertion of a hydrophobic gold precursor into the mesopores of RMSN was reached through a micellar solubilization mechanism and gold nanoparticles were achieved through a thermal reduction. The resulting RMSN and Au-RMSN samples were characterized by using X-ray diffraction, transmission and scanning microscopies (TEM and SEM), X-ray photoelectron spectroscopy (XPS), nitrogen physisorption and solid-state Nuclear Magnetic Resonance (NMR). The interaction of Au precursor (a carbene complex) with the thiol group at the silica surface was identified and found to play a crucial role in the dispersion of the uniform metal nanoparticles at the internal surface of RMSN. Moreover, TEM micrographs revealed the absence of large gold particles outside the mesopore network. The shape of Au nanoparticles and their loading amount in the mesoporous silica could be easily tuned by altering the concentration of gold precursor.     

Formation and healing of micrometer-sized channel networks on highly mobile Au(111) surfaces

Practical protocols are presented to reproducibly prepare micrometer-sized Au(111) substrates. Au(111) terraces of micrometer dimensions and atomic smoothness were crystallized by flame-annealing vacuum-deposited gold films on glass and on millimetric amorphous gold shots. Gold films and shots that were slowly cooled in a moderately applied stream of nitrogen gas exhibited large and stable crystal surfaces with Au(111) morphologies. Similarly, flame-annealed gold samples cooled with another protocol--in much rougher streams of nitrogen gas--produced morphologically unstable and highly mobile Au(111) layers. Within the first hour after preparation, however, rapid microscale restructuring in the layers produced complex morphologies of hexagonal channel networks and islands that were predominantly triangular. These channeled gold layers fused slowly in the following hours, with velocities of 0.01-0.2 A/s, as quantified by digital image correlation (DIC). Atomically smooth, stable, and predominantly triangular Au(111) terraces on the scale of micrometers were observed approximately 24 h after the sample preparations.     

焙烧方法和焙烧条件对纳米Au/HZSM-5催化剂金粒径和催化性能的影响

采用负压沉积沉淀法制备了纳米Au/HZSM-5催化剂前体,研究了深床焙烧和等离子体焙烧两种方法,以及焙烧温度和焙烧气氛对催化剂中纳米金粒径和催化性能的影响,并采用ICP、TEM、XRD、UV-vis、XPS等表征方法对催化剂金粒子进行了物化性能表征,采用合成气羰基化制乙酸甲酯反应表征催化性能。结果表明,不同焙烧方法和不同焙烧温度及气氛对负载型纳米Au/HZSM-5催化剂中金粒径、形貌、物化性质和催化性能有明显影响。其中,以等离子体焙烧方法在500℃氮气气氛下制备的纳米1.86%Au/HZSM-5催化剂中的金粒径最小,为2-5 nm。用于催化合成气羰基化制乙酸甲酯反应,原料中CO的转化率为67%,乙酸甲酯选择性可达78%。     

Highly selective electrochemical method for the detection of serotonin at carbon fiber microelectrode modified with gold nanoflowers and overoxidized polypyrrole

A gold nanoflowers and overoxidized polypyrrole modified carbon fiber microelectrode (OPPy/Au NFs/CFME) was fabricated using electroless deposition and electrochemical method for highly selective and sensitive detection of 5-HT.     

Highly selective electrochemical method for the detection of serotonin at carbon fiber microelectrode modified with gold nanoflowers and overoxidized polypyrrole

A highly selective and sensitive electrochemical method was developed for the detection of serotonin (5-hydroxytryptamine, 5-HT) at gold nanoflowers (Au NFs) and overoxidized polypyrrole (OPPy) modified carbon fiber microelectrode (CFME). Carbon fiber was firstly modified with gold nanoflowers using electroless deposition method, and then modified with overoxidized polypyrrole using electrochemical polymerization and overoxidization to obtain OPPy/Au NFs/CFME. The obtained OPPy/Au NFs/CFME was characterized by field emission scanning electron microscopy and electrochemical techniques. It was found that the OPPy/Au NFs/CFME showed good sensitivity for the detection of 5-HT in the range of 10 nmol/L − 7.0 μmol/L with detection limit of 2.3 nmol/L, and negligible interferences from ascorbic acid, 5-hydroxyindole acetic acid and uric acid. The OPPy/Au NFs/CFME was successfully applied to the detection of 5-HT in human serum samples with good recovery. The work demonstrates that the electrochemical method, incorporating signal amplification of Au NFs with higher cation selection of OPPy, provides a promising tool for the detection of 5-HT in biological systems     

Tricarbonyls of low-coordinated Au(0) atoms in zeolite-supported gold nanoparticles: Evidence from infrared and X-ray absorption spectroscopies

Mononuclear gold complexes in zeolite NaY were synthesized from initially physisorbed Au(CH3)2(C5H7O2) and characterized by X-ray absorption and infrared spectra recorded as the samples were exposed to flowing CO. X-ray absorption spectra demonstrate the formation of zero-valent gold nanoparticles during the CO treatment. Three new nu(CO) bands grew in during this treatment, at 2070, 2033, and 2000 cm(-1), characteristic of carbonyls of Au0. Because the relative intensities of these bands decreased monotonically when the flow of CO was replaced by flowing He, it is inferred that they correspond to a single Au0(CO)3 species, on low-coordinated Au atoms. This is the first example of an Au0(CO)3 species.