POLYORGS as complexing sorbents for preconcentration of trace metals

Summary The main characteristics of the complexing sorbents POLYORGS are reviewed. These sorbents contain pyrazole, imidazole, amidoxime, 2-mercaptobenzothiazole, thioglycolanilide and arsenazo groups and exhibit high selectivity in respect to noble, rare-earth and heavy metals. The sorbents POLYORGS are applied for the preconcentration of these metals to be determined in ores, rocks, natural and waste waters, and industrial products. The metal determinations after preconcentration are carried out by means of different instrumental methods (e.g., AAS, XRFA, ICP-AES, NAA) either directly in the sorbent, after elution of the analytes or decomposition of the sorbent.     

Determination of osmium by the sorption-X-ray fluorescence technique

Sorption of osmium(IV, VI) on complexing sorbents POLYORGS XXIV, POLYORGS 32 M, and POLYORGS 32 V and on the PVA-PGMA-PEPA sorbent from alkaline and hydrochloric acid solutions is studied. It is demonstrated that equilibrium in systems under study is attained within 40 min for the POLYORGS XXIV sorbent and within 2.5 h for the POLYORGS 32 V sorbent and that the sorbents exhibit a sufficiently high sorptive capacity with respect to osmium: from 3.4 to 8 mg of Os(VI) in alkaline solutions and 2.2 mg of Os(IV) in acidic solutions. Optimal conditions of analysis of a concentrate on an EDX-771 energy-dispersive X-ray fluorescence spectrometer are revealed and, on this basis, a sorption-X-ray fluorescence method that provides the determination of osmium in a wide concentration range with the detection limit down to 10^-6% is developed.     

Properties of new fibrous adsorbents with amidoxyme and hydrazidine groups

Data on sorption properties of new fibrous adsorbents with respect to heavy metals are presented. The POLYORGS 34 and POLYORGS 35 filled fibrous adsorbents and POLYORGS 33 fibrous adsorbent contain amidoxyme and hydrazidine groups. Is has been shown that these adsorbents can be used for the adsorption preconcentration of heavy, noble, and rare metals and radionuclides from aqueous salt solutions. Examples of using adsorbents under study for the dynamic preconcentration of copper from a 0.5 M NaCl solution during filtration through a series of disks, column, or adsorption cartridges are presented.     

A selective sorbent for concentrating noble metals

New chelating sorbents have been synthesized by aminating chloromethylated styrenedivinylbenzene macroporous copolymers with 3(5)-methylpyrazole. The sorption of noble metals from acid solutions and the selectivity has been studied. The sorbents are of interest for selective concentration and extraction of the noble metals.     

Preconcentration of noble metals with the POLYORGS 4 complexing sorbent under the action of microwave irradiation

The sorption of Au(III), Pd(II), Pt(IV), Rh(III), and Ir(IV) with the POLYORGS 4 complexing sorbent in the static mode was studied at room temperature and on thermal and microwave heating. It was demonstrated that the sorption of noble metals from 1 M HCl and 1 M HNO₃ solutions can be substantially accelerated under the action of microwave irradiation. Based on the obtained data, the conditions of the group preconcentration of noble metals for their subsequent determination by the ETAAS and ICP AES methods were selected. The preconcentration procedure was used for the analysis of certified reference material SARM-7B (platinum-containing ore), VT-1 (copper-nickel sulfide ore), and the alloy of copper with noble metals.     

Sorption preconcentration in combined methods for the determination of noble metals

Combined methods for the determination of noble metals with the use of sorption preconcentration with complexing, anion-exchange, and other sorbents are reviewed. Characteristics of sorbents, techniques of sorption preconcentration, and techniques for the preparation of a concentrate for determination are considered. Features of instrumental methods for the determination of noble metals in the analysis of different materials are discussed. Examples of the use of sorption preconcentration in combined methods for the determination of noble metals are given from publications between 1996–2005.     

Sorption Preconcentration of Platinum-Group Metals with Filled Fibrous POLYORGS Sorbents

The sorption of platinum, palladium, and rhodium with fibrous filled POLYORGS sorbents was studied depending on the concentration of hydrochloric acid and the time of contact of the solution with the sorbent in the batch mode. The equilibrium and kinetic characteristics of the sorption of platinum with the POLYORGS 17-n sorbent were determined, on the basis of these data the conditions for the dynamic preconcentration of platinum from a 1 M HCl solution were calculated. Conditions were selected for the group preconcentration of palladium, platinum, and gold in the dynamic mode and for their subsequent determination in the sorbent. It was demonstrated that rhodium can be preconcentrated with the POLYORGS 17-n sorbent in the dynamic mode in the presence of tin chloride.     

Trends in sorption preconcentration combined with noble metal determination.

Nowadays much attention is being paid to the determination of trace amounts of noble metals in geological, industrial, biological and environmental samples. The most promising techniques, such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS) are characterized by high sensitivity. However, the accurate determination of trace noble metals has been limited by numerous interferences generated from the presence of matrix elements. To decrease, or eliminate, these interferences, the sorption preconcentration of noble metals is often used prior to their instrumental detection. A great number of hyphenated methods of noble metal determination using sorption preconcentration have been developed. This review describes the basic types of available sorbents, preconcentration procedures and preparations of the sorbent to the subsequent determination of noble metals. The specific features of instrumental techniques and examples of ETAAS, FAAS, ICP-AES, ICP-MS determinations after the sorption preconcentration of noble metals are considered. The references cited here were selected mostly from the period 1996 - 2006.     

Metal Sorption by Materials with a Mobile Phase of Extractants

Data on sorption of rare, noble, radioactive, and nonferrous metals from aqueous solutions by impregnates and TVEXs were analyzed. These are materials combining the properties of sorbents and extractants and differing in the production method. Their distinctive feature is that the extractant is not chemically bonded to the solid support, which is responsible for high kinetic characteristics of sorption processes involving these materials, favorably comparing with conventional sorbents. As a mobile phase to be deposited on the carrier (mainly polymeric) in the case of impregnates or to be introduced during synthesis of TVEXs served organophosphorus extractants, amines, quaternary ammonium bases, etc. Information regarding the effect of various parameters (solution acidity, metal concentration, phase ratio, temperature, and concentration of impurity elements) on separating capability and metal sorption capacity and kinetics was provided for this type of materials. Methods used for stabilizing the properties of impregnates with the view to minimize the extractant loss during application were considered.

     

New Complexing Polymer Aminothioether Sorbents in the Analytical Control of Recyclable Metal-Containing Raw Material of Rare and Noble Metals

The development and use of thioether sorbents for the separation and preconcentration of metals from aqueous solutions are described. The possibilities of initial polymer thioethers in selective preconcentration and the acceleration of sorption through the introduction of nitrogen-containing groups into thioethers are considered. The dependence of the selectivity of sorbents on the nature of radical at the nitrogen atom is revealed. The use of aminothioethers with different substituents at the nitrogen atom enables distinguishing the groups of noble metals, toxic elements of arsenic and selenium subgroups, and a number of nonferrous metals in the presence of large excesses of other elements. A high recovery of the elements to be determined into the sorption preconcentrate and the selectivity of the sorbents help to improve the accuracy of the analysis. Prospects for the use of aminothioethers are considered on an example of sewage waters. It is found that the extraction of small concentrations of elements from large volumes of solutions is more convenient to carry out in dynamics, for which powdered aminothioether sorbents are not suitable. To ensure a possibility of using aminothioethers in dynamics, a “snake in a cage” synthesis method is used, in which the inert granular support is modified with aminothioether moieties. The introduction of aminothioethers with different radicals at the nitrogen atom makes it possible to combine sorbents selective with respect to different groups of elements on one carrier and thus to create a universal sorbent with predetermined properties, aimed at extracting certain metals.     

Sorption methods of concentrating noble metals

Summary The possibility of concentrating microamounts of noble metals on inorganic collectors and chelating sorbents has been investigated. Optimum conditions have been found for simultaneous concentration of Pd, Pt, Rh, Ir, Au and Ag from solutions of complicated composition. For trace analysis a method is suggested based on co-precipitation of the noble metals on copper sulphide, with separation from large amounts of Ni, Co, Fe and associated components. For separation of the noble metals from copper, thin-layer chromatography or sorption on a chelating sorbent under static conditions can be used. The purity of the concentrations obtained allows use of various methods of determination: spectral, atomic-absorption, radioactivation etc.

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Zusammenfassung Die Möglichkeit, Edelmetalle in Mikromengen an anorganischen Kollektoren und Chelatbildnern anzureichern, wurde untersucht. Optimale Bedingungen für die gleichzeitige Anreicherung von Pd, Pt, Rh, Ir, Au und Ag aus Lösungen komplizierter Zusammensetzung wurden gefunden. Für spurenanalytische Zwecke eignet sich die Mitfällung von Edelmetallen mit Kupfersulfid, wobei sie von Ni, Co, Fe und sonstigen Begleitstoffen getrennt werden. Zur Trennung von Kupfer kann die Dünnschichtchromatographie oder die Adsorption an Chelatbildnern unter statischen Bedingungen dienen. Die Reinheit der Konzentrate ermöglicht dann die Bestimmung durch Spektralanalyse, Atomarabsorption, Aktivierungsanalyse usw.

     

Ion-exchange resins containing S-bonded dithizone and dehydrodithizone as functional groups : Part 1. Preparation of the Resins and Investigation of the Sorption of Noble Metals and Base Metals

The one-step reaction of dehydrodithizone with chloromethylated polystyrene yields the anion-exchanger P-TD. Reduction of the immobilized tetrazolium groups of P-TD produces a chelating resin, P-D, containing S-bonded dithizone as the functional group. Distribution coefficients as a function of acidity are presented for 27 metal ions, to establish the selectivity of these sorbents for noble metals. For gold and platinum group metals, the ion-exchangers show marked differences in loading capacities, rates of simultaneous sorption in static conditions and efficiencies in column tests. The P-TD anion exchanger seems to be more profitable than the P-D chelating resin for most purposes.     

Sorption Capacity and Selectivity Relative to Metal Ions for Oxidized Carbon Sorbents with Different Numbers of Oxygen-Containing Groups

We have determined the sorption capacity and selectivity for a broad range of metal ions (alkali, alkaline-earth, transition metal, noble metals, etc.) in two-component and multicomponent mixtures of oxidized carbon sorbents with different numbers of oxygen-containing surface functional groups. We discuss the reasons for the observed changes, their connection with the nature and number of oxygen-containing surface functional groups, and the possibilities for practical application.     

New sorbents based on organosilicon guanidine derivatives

Monomeric and polymeric organosilicon derivatives of 1-acetylguanidine, which exhibits sorption properties, were synthesized. The organosilicon polymers prepared were studied as sorbents for heavy [Hg(II)] and noble [Ag(I), Au(III), Rh(III), Pd(II), Pt(IV)] metals. They actively take up platinum group metals and exhibit metallochromic properties by analogy with the starting compound, 1-acetylguanidine. Their interaction with all the elements studied is accompanied by coloration. The initial monomers exhibit similar metallochromic properties.     

Automated on-line preconcentration of palladium on different sorbents and its determination in environmental samples

The determination of noble metals in environmental samples is of increasing importance. Palladium is often employed as a catalyst in chemical industry and is also used with platinum and rhodium in motor car catalytic converters which might cause environmental pollution problems. Two different sorbents for palladium preconcentration in different samples were investigated: silica gel functionalized with 1,5-bis(di-2-pyridyl)methylene tbiocarbohydrazide (DPTH-gel) and [1,5-Bis(2-pyridyl)-3-sulphophenyI methylene thiocarbonohydrazide (PSTH) immobilised on an anion-exchange resin (Dowex lx8-200)]. The sorbents were tested in a micro-column, placed in the auto-sampler arm, at the flow rate 2.8 mL min(-1). Elution was performed with 4 M HCl and 4 M HNO3, respectively. Satisfactory results were obtained for two sorbents.     

New organosilicon derivatives of some analytical reagents: sorbents and metallochromic agents

A synthesis of organosilicon monomeric and polymeric derivatives of 1,4-phenylenediamine, 4-aminoantipyrine, and aniline, which are analytical agents possessing sorption properties, was accomplished. The synthesized organosilicon polymers were studied as sorbents of heavy metals Fe^III, Hg^II and noble metals Ag^I, Au^III, Rh^III, Pd^II, Pt^IV. Poly[(3-N-silsesquioxanylpropyl-4aminoantipyrine)] exhibited high sorption activity with respect to platinum group metals in comparison with poly[N,N´-bis(3-silsesquioxanylpropyl)-1,4-phenylenediamine]. The reaction of poly[(3-N-silsesquioxanylpropyl-4-aminoantipyrine)] practically with all the elements under study was accompanied by coloring. The starting monomer exhibited similar metallochromic properties.     

New carbofunctional organosilicon monomers and polymers possessing sorption and metal chromatic properties

Monomeric and polymeric β-naphthylamine and dithizone organosilicon derivatives were synthesized. The organosilicon polymers were studied as sorbents of heavy (Fe^III, Hg^II) and noble (Ag^I, Au^III, Rh^III, Pd^II, Pt^IV) metal ions, as well as of Ce^III and Tb^III. They were found to possess high sorption activity toward platinum group metals and iron. The monomers and polymers obtained exhibit metal chromatic properties. Their reactions virtually with all the elements studied, except cerium and terbium, are accompanied by coloration.     

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), ¶Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 μg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.     

Surface Atomic Regulation of Core–Shell Noble Metal Catalysts

Core–shell noble metal catalysts have gained significant attention in the past few decades, as they not only reduce the use of noble metals effectively but also exhibit unique properties derived from the synergistic effect between core and shell metals. In particular, regulating the surface structure of shells to maximize the atomic utilization efficiency of noble metals is critically important. Controlling the shell thickness of noble metal catalysts at the atomic level as an efficient approach to realize this goal has been attracting growing attention; this approach involves the formation of ultrathin shells (typically 2–6 atomic layers), monolayers, or even atomically dispersed noble metals embedded in the host metal. These strategies drive the core/support metals to improve the number of active sites and the intrinsic activity of the deposited noble metals remarkably, meanwhile minimizing the usage of noble metals. Herein, recent advances regarding atomic control of the core–shell noble metal catalysts is reviewed, with focus on the surface regulation. First, synthesis methods and surface structures are summarized, and then catalytic applications of these architectures are highlighted.     

Trends in Sorption Recovery of Platinum Metals: A Critical Survey

The major trends in research into the sorption recovery and separation of platinum metals are critically surveyed. The advantages and disadvantages are described for ion-exchange and complexing sorbents based on organic polymers, chemically modified silicas, sorbents with applied macrocyclic compounds, hybrid organomineral sorbents with supported polymers, molecular imprinted sorbents, solid-phase extractants based on ionic liquids, biosorbents, and other types of sorbents. The technological potentials of these sorbents are evaluated.