Radiochemical fire-assay for determination of the platinum group elements

The radioactive study of Ni–NiS bead fire-assay followed by neutron activation analysis showed nearly quantitative collection of the platinum group elements and gold in the bead. However, there was clearly some loss of gold and ruthenium at the dissolution and filtration stage. A preliminary study of the radiochemical fire-assay method indicates that the technique could overcome the problem of losses. Chemical carrier behaves in the same way as platinum metal concentrate during the analytical procedure and could be used to evaluate yields during each determination. When applied to rock samples, the radiochemical fire-assay gives good sensitivity and could be applied to the determination of nanogram concentrations of the platinum group elements without the problem of high blank values from reagents.     

A survey of the determination of the platinum group elements

The platinum-group metals (PGMs), Ru, Rh, Pd, Os, Ir and Pt, are widely used as catalysts in petroleum and chemical processes. They find wide applications in automotive exhaust-gas control converters and are of immense importance to the electronics industry. They are found in many items of jewellery and serve to an increasing extent as a form of investment. The PGMs are extracted in minute quantities from a limited number of ores, found mainly in S. Africa and the USSR. They are concentrated and separated from each other by elaborate chemical processes. Because of their great intrinsic value (Pt $650 per oz; Rh $1400 per oz), the recycling of the PGMs from literally hundreds of different forms of scrap is an essential factor in the overall management of the PGM economy. In this survey emphasis is placed on the need to tailor the analytical method according to (a) the environment in which the PGMs occur, (b) the individual PGM concentrations, and (c) the desired sensitivity and precision. The factors which determine the choice of chemical, physicochemical and/or instrumental approaches are discussed. They are further commented on in extensive presentations of dissolution and separation techniques and methods for the final measurement of individual PGMs. Appendices are provided which present the compositions and sources of the products most frequently encountered in PGM analysis, along with information on methods of decomposition, separations required, type of separation, and final determination.     

Recent advances on carborane-based ligands in low-valent group 13 and group 14 elements chemistry

Carboranes are a class of polyhedral boron-carbon molecular clusters, they can serve as versatile ligands in stabilizing low-valent main group element compounds, due to their exceptionally thermal and chemical stabilities, easy modifications at the cage carbon vertices, as well as large spherical steric effects. These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity, which indeed enrich the ...     

Recent advances in integrating platinum group metal-free catalysts in proton exchange membrane fuel cells

Platinum group metal (PGM)-free catalysts are promising low-cost materials for the oxygen reduction reaction in proton exchange membrane fuel cells (PEMFCs). A variety of chemical precursors and synthesis methods have been proposed to increase their catalytic activity. In comparison, significantly less attention has been dedicated to the integration of these PGM-free catalysts into operating electrodes by investigating the role of the membrane electrode assembly (MEA) fabrication on the PEMFC performance. We discuss here some remarkable performance improvements recently achieved by tuning catalyst loading, ionomer content, and ink solvent composition, and call for further explorations of the ink processing and MEA fabrication to improve performance.     

Direct and simultaneous determination of metal impurities in catalysts based on platinum group elements

Production of new catalysts requires effective analytical quality control. The study of trace element composition of heterogeneous catalysts, based on C+PdO, using atomic emission spectrometry (AES) was carried out. A new method for the direct solid-state analysis by means of AES with direct current arc discharge was developed. On the basis of the qualitative analysis of elements, Al, Fe, Ni, Si and Ti have been identified, and for these elements, the quantitative method of determination has been developed. Optimization of excitation parameters and validation of the analytical method are presented. Calibration samples of the following composition were prepared: graphite powder (as a matrix), 3% of PdO and increasing contents of determined element oxides (spectrally pure). Calibrations were calculated by means of the least squares method. Working range for element impurities was from 1% to 0.0003%, and the limits of quantification — LOQ, (10-σ criterion) varied in the range from 0.002% (Ti) to 0.0038% (Si). For the control of active component, palladium was calibrated (working range — 0.01%–10.00%; LOQ ?0.027%). The developed method can be used, also, for the elemental determinations of the other carbon based catalysts with the different active components (of platinum group elements).      

Recent advances in solid-phase extraction of platinum and palladium

Increasing platinum concentrations have been detected in environmental samples since the introduction of catalytic converters used in cars. Also the intensive use of platinum-based anti-tumor drugs led to interest in the determination of trace amounts of platinum absorbed by the human body and of the physiological effect of its complexes on living organism. However, detection of Pt and Pd in environmental and biological samples with complex matrices, has to be generally preceded by a preconcentration/separation step. A brief overview of the application of solid sorbents for these procedures based on published data is presented. Attention is also paid to preparation of the samples and detection methods usually used for determination of platinum and palladium.     

电感耦合等离子体质谱（ICP-MS）法测定碳质板岩样品中铂族元素

碳质板岩属黑色岩系,与多种金属(包括贵金属)成矿有密切的联系。按照常规的分析方法,硫镍试金溶剂配方都不能对贵金属元素有较好的富集,影响贵金属元素的测定。根据石墨岩中样品的成份特征,对测定铂族元素的常规硫镍试金配方进行了改进,增加了硝酸钾和氧化镁,且无需加入锇稀释剂。通过实验选择了合适比例配料,熔融后粉碎镍扣,加入盐酸分解,碲共沉淀剂富集。过滤沉淀用王水溶解。用电感耦合等离子体质谱(ICP-MS)法测定,Lu作内标,对碳质板样品中的铂族元素进行了测定。结果表明,加标回收率为85%～105%,能够满足碳质板岩中铂族元素的分析测定要求。     

Methods for the determination of platinum group elements originating from the abrasion of automotive catalytic converters

Anthropogenic emission of platinum group elements (PGEs) from the abrasion of automotive catalytic converters into the environment has significantly increased. However, the concentration level of these PGEs (i.e. Pd, Pt, Rh) is still very low in the nature. Accordingly, their determination and speciation in various environmental compartments appears to be a challenging task for analytical chemists. The present review gives an overview of the analytical procedures documented in this particular field of analytical chemistry with a distinctive emphasis on spectrochemical methodology, it being the most sensitive and robust for accomplishing the above analytical task.     

Recent advances in the analytical chemistry of the transplutonium elements

A survey is given of current developments in the determination of the transplutonium elements, and of the properties useful in their analytical chemistry.     

Distribution and speciation of platinum group elements in environmental matrices

The use of platinum group elements (PGEs) as components of autocatalytic converters attached to motor vehicles has resulted in serious contamination of the environment by Pt, Rh and Pd in nanocrystalline forms. Trace concentrations of PGEs, particularly the major component Pt, in environmental samples have been measured by sensitive instrumental procedures. These data have raised further questions about the nature of Pt species in contaminated soils and in plants grown in them. The focus of attention is changing from accumulations of data expressing total concentrations to investigations of speciation. Application of analytical procedures for research on speciation has provided information concerning transformations of Pt compounds in contaminated soils, the uptake of Pt by plants and the nature of Pt compounds in vegetation. Determination of background levels of precious metals in clinical and environmental matrices has required the development of analytical methods which combine uses of minimal quantities of reagents, and as small a number of chemical operations as possible to yield very low procedural blanks. Sensitive instrumental methods based upon high resolution inductively coupled plasma mass spectrometry and adsorptive stripping voltammetry have proven to be valuable for this work.     

Quantitative bioimaging of platinum group elements in tumor spheroids

Limited drug penetration into tumor tissue is a significant factor to the effectiveness of cancer therapy. Tumor spheroids, a 3D cell culture model system, can be used to study drug penetration for pharmaceutical development. In this study, a method for quantitative bioimaging of platinum group elements by laser ablation (LA) coupled to inductively coupled plasma mass spectrometry (ICP-MS) is presented. Different matrix-matched standards were used to develop a quantitative LA-ICP-MS method with high spatial resolution. To investigate drug penetration, tumor spheroids were incubated with platinum complexes (Pt(II)acetylacetonate, cisplatin) and the palladium tagged photosensitizer 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin (mTHPP). Distribution and accumulation of the pharmaceuticals were determined with the developed method.     

Solid-phase extraction in the determination of gold, palladium, and platinum

A simple classification of various sorbents and solid-phase extraction procedures used for preconcentration of trace levels of Au, Pd, and Pt from different sample types is proposed in this review article. The large variety of available sorbents/procedures has been organized according to expected mechanisms of sorption process (complex formation; ion exchange; adsorption; ion-imprinted or molecularly imprinted polymers); according to the kind of monomeric units of the polymer matrix as well as on the basis of the kind of functional group responsible for main performance characteristics (selectivity, capacity) of the sorbent. Advantages of chemically modified sorbents, sulfur-containing sorbent extractants, and ion-imprinted polymers, together with rational pretreatment by means of microwave treatments, scaling down of enrichment, and quantification by means of flow and flow injection approaches are given. Preferred instrumental techniques for quantification of ppb levels of Au, Pd, and Pt in prepared concentrates/column eluates are multielement instrumental techniques: inductively coupled plasma optical emission spectrometry (ICP-OES), and inductively coupled plasma mass spectrometry (ICPMS). Excellent limits of detection at picogram levels of these analytes are provided by electrothermal atomic absorption spectrometry (ETAAS), generally in single-element mode and the neutron activation analysis (NAA), while X-ray fluorescence spectrometry and flame AAS are rarely applied because of lack of sensitivity at sub-ppm levels of Au, Pd, and Pt. Some problems of atomic spectrometric quantification techniques and their representative limits of detection are given. Recent applications to geological, industrial, pharmaceutical, biological, and other materials are tabulated. References have been selected mostly from the period 1995 to 2010.     

On the determination of platinum group elements in environmental materials by inductively coupled plasma mass spectrometry and microwave digestion

The interferences from Cd, Cu, Hf, Pb, Sr, Zn, Zr and Y on the inductively coupled plasma quadrupole mass spectrometry (ICP-MS) determination of Pt, Pd, Rh, Ru and Ir in geological (Pt-ore SARM-7, abundance range for platinum metals 0.07-3.74 μg/g) and environmental samples (sediment JSd-2 abundance range for Pt and Pd 0.0167-0.021 μg/g; road dust and plant sample) are evaluated using model solutions, real samples and comparison to inductively coupled plasma atomic emission spectrometry (ICP-AES) results. Pt, Rh, Ru and Ir can be determined usually after introduction of corrections for the interference in all investigated materials though in sediments the direct determination of Pt might be a problem depending on the actual Hf concentrations. The direct determination of Pd (after microwave-assisted acid digestion) is possible in ores using all investigated isotopes (, , ), in plants using and correction for the interferences of Zr, Mo and Cd, and not possible in sediments and road dust. Therefore, we developed a procedure for isolation of Pd using its diethyl-dithio-carabamate (DDTC) complex. The detection limits for Pt, Pd and Ir are 0.015 ng/g, and for Ru and Rh 0.03 ng/g.     

Recent advances in the structural determination of endohedral metallofullerenes

The structural determination of endohedral metallofullerenes has attracted special attention in disclosing the formation mechanism and developing new routes to bulk production. Recent advances in the theoretical and experimental studies are summarized with representative mono- and dimetallofullerenes such as M@C₈₂ (M=Ca, Sc, Y, and La), Sc₂@C₈₄, and La₂@C₈₀. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 232–239, 1998     

The determination of all the platinum group elements and gold in rocks and ore by neutron activation analysis after preconcentration by a nickel sulphide fire-assay technique on large samples

The noble metals are inhomogeneously distributed in sulphide ores and their host rocks. It is therefore necessary to analyse large sample sizes to obtain representative analyses. A nickel sulphide fire assay technique has been adapted to extract the noble metals from a large sample size (50 g) into a nickel sulphide button. Subsequently the fire assay button is dissolved in hydrochloric acid and the solution is filtered. The noble metal residue retained on the filter paper is analysed quantitatively by i.n.a.a. techniques. This method is rapid, relatively inexpensive and has better sensitivities for all the noble metals than other analytical techniques.     

Determination of platinum group elements and gold in geological materials: a review of recent magnetic sector and laser ablation applications

Inductively coupled plasma mass spectrometry (ICP-MS) has been used extensively as a rapid and accurate instrumental technique for determinations of platinum group elements (PGEs) and gold. Methods based upon ICP-MS have been important in analyses of many types of samples, and especially of geological materials containing very low concentrations of these elements. Recently, analytical methods based upon ICP-MS have been improved and widened in scope by the introduction of new magnetic sector (or high resolution) spectrometers, and laser ablation (LA) sampling. Detection limits attainable for PGEs and Au using magnetic sector instruments in analytical procedures cited here are as low as 0.01-0.02 pg g⁻¹; instruments have a dynamic range of up to nine orders of magnitude. This review describes applications of the techniques to analyses of PGEs and gold in minerals, nodules, meteorites, ice, sediments, airborne particulates and reference materials. The period covered is 1998-2002.     

Intermetallics and alloys of transplutonium elements with metals of the platinum group

Americium and curium alloys with palladium and platinum containing up to 20% of actinide were prepared by the coupled reduction technique. The alloys obtained were investigated by X-ray, differential thermal analysis and metallography. Phase diagram sections for Pd–Am, Pd–Cm, Pt–Am and Pt–Cm systems have been constructed. Intermetallics Pt₅An (An=²⁴³Am,²⁴⁴Cm,²⁴⁹Bk,²⁴⁹Cf), Ir₂ ²⁴⁹Bk and Rh₃ ²³⁹Bk were obtained as thin layers on the surfaces of metallic substrates. X-ray investigation has shown that Pt₅An compounds have hexagonal structures of the Cu₅Ca-type, Ir₂Bk- cubic lattice of the Cu₂Mg-type and Rh₃Bk intermetallic has fcc lattice of the Cu₃Au-type. The influence of intensive -decay of transplutonium nuclides on the crystal structure of the intermetallics prepared has been investigated.     

Impact of ageing on the distribution of platinum group elements and catalyst poisoning elements in automobile catalysts

The distribution of platinum group elements (PGEs) and catalyst poisoning elements (Pb, Zn, P and S) on the surface of gasoline and diesel automobile catalysts was investigated within this study. Laser ablation–inductively coupled plasma mass spectrometry (LA–ICPMS) provides both the sensitivity and the spatial resolution required for the surface analysis of sectioned automobile catalysts, and scanning along channels reveals the distribution of longitudinal changes in PGE and catalyst poisoning elements. Changes in catalyst surface features were studied for fresh catalysts and after ageing of the catalyst up to 80 000 km for both types of catalysts studied. The PGEs in the gasoline catalyst were found to decrease at the front of the catalyst after ageing, whereas the diesel catalyst presented a more constant loss along the catalyst. The fraction of poisoning elements (Pb, P and Zn for the gasoline catalyst and P and Zn for the diesel catalyst) retained by the catalyst is distributed non‐uniformly over the length of the catalyst. This could indicate different ageing mechanisms for gasoline and diesel catalysts. Copyright © 2003 John Wiley & Sons, Ltd.     

An accurate procedure for the determination of low levels of platinum group elements in standard materials by neutron activation analysis

The paper describes a destructive neutron activation procedure for the determination of all platinum group elements (PGE). Only a few steps are required after irradiation, namely sample dissolution, osmium and ruthenium separation by solvent extraction, anion exchange separation of remaining noble metals and counting. The chemical yield is evaluated. The method has been used for the determination of noble metals in a large variety of standard reference materials, mainly of geological and technological origin. The results, given as the average of four independent analyses are reported and discussed. Average precision for the whole procedure is usually below 8% and sensitivities are adequate to meet the analysis requirements of terrestrial PGE- and Au-poor materials.