A review of the radiation stability of ion exchange materials

A comprehensive literature survey on the radiation stability of ion exchangers resulted in the publication of an extensive data compilation on the effects of ionizing radiation on synthetic organic ion exchangers in this journal (Vol. 97, No. 1). This paper is a brief review of the majorfindings of this literature survey along with similar information on synthetic inorganic ion exchangers. The primary goal of this literature survey is to review present knowledge on the effects of ionizing radiations on synthetic ion exchange materials used in radiochemical processing. Although there are gaps in our knowledge of the mechanisms of radiolytic changes in ion exchangers, the information available in the literature shows some general trends and similarities in observed qualitative effects by different types of organic and inorganic ion exchange materials. These trends and observations have been formulated into a set of qualitative and semi-quantitative statements that can be useful to potential users of ion exchange materials in nuclear material processing and radioactive waste management. Present knowledge, of the behavior of ion exchangers under the influence of ionizing radiations is too limited to justify quantitative predictive modeling.     

Characteristics of Novel Types of Substituted Cerium Phosphates

The disodium, dilithium, dipotassium and distrontium forms of cerium phosphate were prepared from their corresponding mono-forms. The chemical content of these inorganic ion exchangers have been characterized by inductively coupled plasma (ICP) spectroscopy. The ion exchange properties of these cation exchangers, their chemical stability and selectivity for certain ions were investigated. It was found that, by introducing different salts into the reaction mixture used to prepare cerium phosphate, robust cation exchange materials of reproducible composition with a good cation capacity, and suitable for column use, are produced. All the ion exchangers with the exception of CeP (dipotassium) show excellent selectivity towards certain cations, thereby increasing the potential practical applications of these inorganic exchangers.     

Dynamic Phosphorus: Thiolate Exchange Cascades with Higher Phosphorothioates

In this study, we introduce phosphorus, a pnictogen, as an exchange center for dynamic covalent chemistry. Cascade exchange of neutral phosphorotri- and -tetrathioates with thiolates is demonstrated in organic solvents, aqueous micellar systems, and in living cells. Exchange rates increase with the pH value, electrophilicity of the exchange center, and nucleophilicity of the exchangers. Molecular walking of the dynamic phosphorus center along Hammett gradients is simulated by the sequential addition of thiolate exchangers. Compared to phosphorotrithioates, tetrathioates are better electrophiles with higher exchange rates. Dynamic phosphorotri- and -tetrathioates are non-toxic to HeLa Kyoto cells and participate in the dynamic networks that account for thiol-mediated uptake into living cells.     

Inorganic Ion Exchangers for Cesium Removal from Radioactive Wastewater

Ion exchange is a proven process for radioactive wastewater decontamination, where inorganic sorbents are ideal due to their thermal, chemical and radiation stability. This review focuses on the removal of Cs⁺ by inorganic exchangers, viz. zeolites, titanosilicates, hexacyanoferrates metal oxides and hydrous metal oxides, bentonite/clays and the key family of ammonium phosphomolybdates (AMPs). The design of new selective composites is also addressed focusing on those based on AMPs, hexacyanoferrates and titanosilicates/zeolites. Future inorganic Cs⁺ exchangers will encompass promising solids, like lanthanide silicates, sodium titanates and metal sulfides. The sensing ability derived from the photoluminescence properties of lanthanide silicates and the efficiency of layered gallium-antimony-sulfide materials in acidic and basic solutions disclose considerable potential for real applications. The ion exchange systems are discussed in terms of sorbent capacity and selectivity (with competitors), pH, temperature and solution salinity. The microscopic features of the exchangers and the associated mechanisms (e.g., pore size, counterions radii, dehydration energy of the ions, coordination environments in the solid exchanger, and site accessibility) are always used for interpreting the ion exchange behavior. On the whole, more than 250 publications were reviewed and a large compilation of data is provided in Supplemental Material.     

Is there a future for biomonitoring of elemental air pollution? A review focused on a larger-scaled health-related (epidemiological) context

The present paper focuses on biomonitoring of elemental atmospheric pollution, which is reviewed in terms of larger-scaled biomonitoring surveys in an epidemiological context. Based on the literature information, today’s availability of solar-powered small air filter samplers and fibrous ion exchange materials is regarded as adequate or an even better alternative for biomonitor transplant materials used in small-scaled set-ups, but biomonitors remain valuable in larger-scaled set-ups and in unforeseen releases and accidental situations. In the latter case, in-situ biomonitoring is seen as the only option for a retrospective study: biomoniors are there before one even knows that they are needed. For biomonitoring, nuclear analytical techniques are discussed as key techniques, especially because of the necessary multi-element assessments in both source recognition and single-element interpretation. To live up to the demands in an epidemiological context, larger-scaled in-situ biomonitoring asks for large numbers of samples, and consequently, for large total sample masses, this all to ensure representation of both local situations and survey area characteristics. Possibly, this point should direct studies into new “easy-to-sample” biomonitor organisms, of which high masses and numbers may be obtained in field work, rather than continue with biomonitors such as lichens. This also means that both sample handling and processing are of key importance in these studies. To avoid problems in comparability of analytical general procedures in milling, homogenization and digestion of samples of large masses, the paper proposes to involve only few but high-quality laboratories in the total element assessment routines. In this respect, facilities that can handle large sample masses in the assessment of element concentrations are to be preferred. This all highlights the involvement of large-sample-volume nuclear facilities, which, however, should be upgraded and automated in their operation to ensure the necessary sample throughput in larger-scaled biomonitoring.     

Outlines of the ion exchange characteristics of hydrous oxides

This work gives a critical review of the behaviour of hydrous oxides as ion exchangers. The various physicochemical properties of this important class of adsorbents and the effect of preparation procedures are summarized. Data on the ion exchange kinetics and thermodynamics are presented and discussed. Selectivity is also discussed in terms of the different parameters. Both aqueous and mixed media are considered. In addition, the different sorption mechanisms, some relevant sorption models, and potential applications in chemical separations are given. Moreover, this review attempts to point to the experimental and theoretical confusions now alarmingly met in the literature.     

Effect of the degradation of ion-exchange resins on the quality of high-purity water prepared by ion-exchange deionization

In the course of water deionization on ion-exchange filters of mixed action, charged with a mixture of KU-2×8 ch.s. cation exchanger and AV-17×8 ch.s. anion exchanger, which are ion-exchange resins of nuclear class, the water being treated is contaminated with soluble organic substances originating from degradation of the resins. Their concentration can reach 20 µg L–1, gradually decreasing to 5–6 µg L–1. Procedures were suggested for determining soluble organic substances washed out from the ion-exchange filters, including gravimetric determination of their sum in aqueous extracts from the organic ion exchangers, spectrophotometric determination in water being purified on the ion exchangers, and preconcentration of electrically charged forms of soluble organic substances by electroosmosis.     

The isotope exchange depth profiling (IEDP) technique using SIMS and LEIS

The determination of the mass transport kinetics of oxide materials for use in electrochemical systems such as fuel cells, sensors and oxygen separators is a significant challenge. Several techniques have been proposed to derive these data experimentally with only the oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry (SIMS) providing a direct measure of these kinetic parameters. Whilst this allows kinetic information to be obtained, there is a lack of knowledge of the surface chemistry of these complex processes. The advent of low-energy ion scattering (LEIS) now offers the opportunity of correlating exchange kinetics with chemical processes at materials atomic surfaces, giving unprecedented levels of information on electrochemical systems with isotopic discrimination. Here, the challenges of these techniques, including sample preparation, are discussed and the advantages of the combined approach of SIMS and LEIS illustrated with reference to key literature data.     

Synthesis,properties and effect of ionizing radiation on sorption behavior of iron silico-antimonate

Incorporation of iron oxide into silico-antimonate of different Si/Sb molar ratios introduced a class of dual salts ion exchangers with advanced ion exchange properties. Physicochemical and equilibrium studies have been carried out to understand the ion exchange properties of these materials. Apparent investigation indicated that iron incorporation into silico-antimonate yields materials having excellent mechanical properties. On the basis of distribution studies, the materials were found to be highly selective for Sr²⁺ or Ce³⁺ depending on their Si/Sb molar ratios. Diffractogram, thermogram, IR spectra and sorption performance of crystalline FeSiSb (114) indicated that no detectable structural changes after an exposure up to 100 kGy of γ-rays. Effect of reaction temperature on the exchange process was investigated and the respective thermodynamic parameters were calculated.     

Synthesis and thermal stability of some inorganic ion exchangers based on silicon and tin

A number of silicon-based inorganic ion exchangers were synthesized under different conditions of preparation. The original and regenerated ion exchange capacities (IECs) were determined. Thermal stability of these materials was investigated in the temperature range of 40?C800?°C. The gain/loss of IEC was studied as a function of temperature. These exchangers show a higher IEC and its retention to a considerable extent at elevated temperatures when compared to that of corresponding ion exchangers which do not contain silica. The thermogravimetric curve shows greater percent mass loss in H⁺ form of the exchanger than in K⁺ form. Dehydration studies seem to throw some light on the state of water molecules present in various samples. The empirical formula and the tentative structure for stannic arseno silicate have also been proposed.     

Controlled porosity monolithic material as permselective ion exchange membranes

Ion exchange membranes (IEMs) are used in a variety of analytical devices, including suppressors, eluent generators and other components used in ion chromatography. Such membranes are flexible and undergo substantial dimensional changes on hydration. Presently the push to miniaturization continues; a resurgent interest in open tubular ion chromatography requires microscale adaptation of these components. Incorporating IEMs in microscale devices is difficult. Although both macroporous and microporous ion exchange materials have been made for use as chromatographic packing, ion exchange material used as membranes are porous only on a molecular scale. Because such pores have vicinal ion exchange sites, ions of the same charge sign as those of the fixed sites are excluded from the IEMs. Monolithic polymers, including ion exchangers derived therefrom, are presently extensively used. When used in a separation column, such a monolithic structure contains an extensively connected porous network. We show here that by controlling the amount of porogen added during the synthesis of monolithic polymers derived from ethylene dimethacrylate – glycidyl methacrylate, which are converted to an anion exchanger by treatment with trimethylamine, it is possible to obtain rigid ion exchange polymers that behave like IEMs and allow only one charge type of ions to pass through, i.e., are permselective. We demonstrate successful open tubular cation chromatography suppressor performance.     

Structural studies on some inorganic ion exchangers

Ferrocyanides of zirconium(IV) and tin(IV), antimonates of cerium(IV) and titanium(IV), and cerium(IV) tungstate, has been shown to be useful materials as inorganic ion exchangers in radio- and analytical chemistry. These materials are sufficiently stable towards high dose of γ-radiations. Attempt is made to study some structural aspects and possible exchange sites of these materials using different techniques like thermal, Mössbauer and infrared spectroscopy.     

Separation of -amino acids using a series of zwitterionic sulfobetaine exchangers

A set of five new covalently bond sulfobetaine exchangers with inner quaternary amines and outer sulfonic acids have been prepared by attachment of a series of zwitterionic precursors to hyperporous divinylbenzene polymers using a grafting reaction. The series of zwitterionic exchangers have the same backbone and identical spacers to the polymeric backbone, as well as comparable capacities. The only difference is the chain length for one to five methylene groups between the charged functional groups. Chromatographic properties are examined by separation of α-amino acids using sodium acetate and nitric acid eluents. The separation mechanism is explored by varying eluent ionic strength and eluent pH, resulting in the conclusion that amino acids are separated due to cation exchange interactions. This is a behavior never before observed using zwitterionic exchangers. It contradicts the fact that sulfobetaine-type materials used in zwitterionic ion chromatography (ZIC) usually are well suited for anion separation and only poorly for cation separation. Contrary to anion separations using the identical set of exchangers, the materials with three and four methylene groups between the charges give the highest retention factors. Materials showing the high potential in ZIC separations of inorganic anions give low retention factors for amino acids and vice versa.     

Transport Properties of Selective Membranes Reversible to Nitrogen-Containing Organic Base Cations: Permeability and Ion Flow

Main transport properties were studied for selective membranes with low dielectric constants based on liquid ion exchangers involving nitrogen-containing organic base cations. Permeabilities and ion flows through a membrane were calculated for major and interfering ions. Dependences of the transport properties of membranes on the concentrations of the ion exchanger and near-membrane solution and their potentiometric characteristics are presented. It was demonstrated that the transport properties of liquid membranes are determined by two main factors: the transfer of counterions through the phase boundary by the extraction–exchange mechanism and the leaching of the ion exchanger from the membrane.     

The Chromatographic Behavior of some Hydrophilic Dyes and Dye Intermediates on Thin Layers of Strong and Weak Ion Exchangers

Abstract

The chromatographic behavior of some polar organic dyes and dye intermediates on thin layers of various forms of cationic and anionic exchange resins has been investigated. The results of this study indicate that the stationary ion and the mobile ion of both types of exchangers greatly affect both the level of tailing and the R_f values of the adsorbed compounds. It is also clear from this study that these resins are more suitable for evaluating the relatively simple dyes containing an SO₃Na group than the higher molecular weight polyazo direct dyes used on cellulosic substrates, and that the Li⁺ and H⁺ forms of the cation exchangers work better than their counterparts. On the other hand, cationic dye molecules require the use of anion exchangers, with the ^?OAc form giving better chromatograms than the C104^? form.     

SYNTHESIS AND APPLICATION OF IMINOCARBOXYLIC CHELATING FIBERS

In this paper,fibrous chelating exchangers with-N(CH2COOH)2 group have been prepared for the first time by a weakly basic anion exchange fiber (aminated fiber)as the starting materials.The fibers were quite effective for the adsorption of heavy metal ion such as Cu^2+.In addition,IR spectrum of the structure of fibers confirms that it is feasible to prepare iminocarboxylic chelating fiber through direct carboxylation reaction.     

Effect of the porous structure of polymer on the kinetics of Ni<Superscript>2+</Superscript> exchange on hybrid inorganic-organic ionites

Hybrid organic-inorganic ion exchangers are obtained by incorporating amorphous zirconium hydrophosphate into the gel of strong acidic cation exchange resin. Hybrid organic-inorganic ion exchangers are obtained by modifying strong acidic cation exchange resin with amorphous zirconium hydrophosphate. The synthesized materials are studied by standard porometry contact. It is found that raising the inorganic component content to 34 wt % diminishes the microporosity of the samples and simultaneously enhances the of meso- and macropore volume. Experiments establish that modification of a polymer matrix lowers the self-diffusion coefficient of Ni²⁺ from 8.1 × 10⁻¹² to 2.4 × 10⁻¹²–4.1 × 10⁻¹² m² s⁻¹; nevertheless, an inorganic ion exchanger minimizes the inhibitory effect of co-ions on the Ni²⁺ → H⁺ exchange rate. One possible mechanism for of filling of the matrix by with particles of zirconium hydrophosphate is discussed.     

Surfactant templated sulfonic acid functionalized silica microspheres as new efficient ion exchangers and electrode modifiers

Porous sulfonic acid functionalized silica spheres have been prepared by oxidation ofthiol-functionalized mesoporous silica samples obtained by co-condensation of (mercaptopropyl)trimethoxysilane and tetraethoxysilane in the presence ofcetyltrimethylammonium as a template. The physicochemical characteristics of the resulting ion exchangers have been analyzed by various techniques and discussed with respect to the amount of functional groups in the materials. Their ion exchange behavior was then studied from batch experiments (determination of cation exchange capacities) and by electrochemistry at carbon paste electrodes modified with these solids. In particular, ion exchange voltammetry applied to two model electroactive cations, Cu2+ and Ru(NH3)6(3+), has pointed out the key role played by the content of organofunctional groups in the materials (which strongly affects their structure and porosity) on their performance as electrode modifiers for preconcentration of target analytes prior to electrochemical detection.     

Pyridine based zirconium(IV) and tin(IV) phosphates as new and novel intercalated ion exchangers

Pyridine based zirconium(IV) phosphate (PyZrP) and tin(IV) phosphate (PySnP) have been synthesized as new and novel intercalated ion exchangers. These materials have been characterized using X-ray, IR spectra, TG, DTG and DTA studies in addition to their ion exchange capacity, elution, pH titration, concentration and distribution behaviour. The distribution studies towards several metal ions in different media/concentrations have suggested that PyZrP and PySnP are selective for Hg(II) and Pb(II), respectively. As a consequence some binary separations of metal ions involving Hg(II) and Pb(II) ions have been performed on a column of these materials, demonstrating their analytical and environmental potential.     

Ligand design for functional metal-organic frameworks

Metal-organic frameworks (MOFs), also known as coordination polymers, are formed by the self-assembly of metallic centres and bridging organic linkers. In this critical review, we review the key advances in the field and discuss the relationship between the nature and structure of specifically designed organic linkers and the properties of the products. Practical examples demonstrate that the physical and chemical properties of the linkers play a decisive role in the properties of novel functional MOFs. We focus on target materials suitable for the storage of hydrogen and methane, sequestration of carbon dioxide, gas separation, heterogeneous catalysis and as magnetic and photoluminescent materials capable of both metal- and ligand-centred emission, ion exchangers and molecular sieves. The advantages of highly active discrete complexes as metal-bearing ligands in the construction of MOFs are also briefly reviewed (128 references).