Superior Ion‐exchange Property of Amorphous Aluminosilicates Prepared by a Co‐precipitation Method

The development of inexpensive inorganic ion‐exchangers for the purification of environmental pollutants is a social demand. Amorphous aluminosilicates with a relatively high homogeneous Al environment are prepared by a feasible co‐precipitation method, i. e., mixing an acidic aluminum sulfate solution and basic sodium silicate solution, which exhibit excellent ion‐exchange selectivity for Cs⁺ and Sr²⁺. The K_d value for Sr²⁺ was comparable with that of zeolite 4A. The local structures and ion‐exchange behavior of the amorphous aluminosilicates are systematically investigated. The ion‐exchange property of the amorphous aluminosilicates can be tuned by changing the interaction between the exchangeable cation and the amorphous aluminosilicates. Also, the amorphous aluminosilicates can adsorb bulky cations that zeolites hardly adsorb due to the limitation of the miropore size of zeolites.     

Synthesis and adsorption investigations of zeolites MCM-22 and MCM-49 modified by alkali metal cations

Ion exchange was made on MCM-22 and MCM-49 zeolites with different Si/Al molar ratios, with Li⁺, Na⁺, K⁺, and Cs⁺ ions and the study of the influence of alkali metal cations on CO₂ adsorption properties was performed. The degree of ion-exchange decreased for larger cations (Cs⁺) apparently due to steric hindrances. The exchange with different cations led to a decrease in the surface area and the micropore volume. Our study shows that the adsorption capacity of the tested zeolites depends significantly on the nature and the concentration of the charge-compensating cations. The highest CO₂ adsorption capacity was obtained on the MWW zeolites with the lowest Si/Al molar ratio and the Li⁺ or K⁺ cations.     

Photophysical and photochemical processes in zeolite cavities: The effects of ion-exchanged alkalimetal cations on the excited states of xanthone and the photolysis of 2-pentanone

The characteristics properties of xanthone phosphorescence and of 2-pentanone photolysis in alkali metal cation-exchanged zeolites have been investigated to clarify the effect of the micro-environment of host-adsorbents on the photophysical and photochemical properties of guest-molecules in restricted void spaces. The enhancement of the phosphorescence yields of xanthone included in zeolites is observed by changing the exchangeablealkali metal cation from Li⁺ to Cs⁺. Simultaneously, the phosphorescence lifetimes were observed to continuously shorten by changing the cation from Li⁺ to Cs⁺. These results suggest that the external heavy-atom effect deriving from the alkali metal cations on the singlet-triplet transitions of xanthone molecules stabilized on alkali metal cations in the order of Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺. The yields for the photolysis of 2-pentanone included in zeolites increase with changing the alkali metal cation from Li⁺ to Cs⁺. IR investigations of the adsorption state of 2-pentanone indicate that strength of the interaction between the alkali metal cations and 2-pentanones decreases by changing the cation from Li⁺ to Cs⁺, which results in a longer lifetime of 2-pentanone. The selectivity of propylene formation is dramatically increased by changing the cation from Li⁺ to Cs⁺. The enhanced formation of propylene is asociated with the hydrogen absorption from propyl radicals by lattice oxygen, their basicity increasing by changing the cation from Li⁺ to Cs⁺. Thus, these changes in the zeolite cavities modified by exchanging cations caused significant effects not only on the excited state but also on the following chemical reactions of ketones.     

Hexacyanoferrate-based composite ion-sensitive electrodes for voltammetry

Composite electrodes made of graphite, paraffin and metal hexacyanoferrates exhibit a voltammetric response of the hexacyanoferrate ions, the potential of which depends linearly on the logarithm of concentration of alkali and alkaline-earth metal ions. This behaviour has been observed on account of the fact that the electrochemical reaction is accompanied by an exchange of these ions between the solution and the zeolitic lattice of the hexacyanoferrates for charge compensation. The voltammetric determination of the formal potential of these electrodes in a solution allows the quantitative analysis of the ions which are exchanged between the metal hexacyanoferrates and the aqueous solutions. Iron(III), copper(II), silver(I), nickel(II) and cadmium(II) hexacyanoferrates have been studied for the determination of H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH⁺₄, Mg²⁺, Ca²⁺ and Ba²⁺. In some cases, the selectivity constants are as low as 310^-4, or even so small that their exact value is inaccessible. Electrodes made of iron (III), copper (II), silver (I), nickel (II) and cadmium (II) hexacyanoferrates are most suitable for the determination of potassium ions. Electrodes with nickel (II) and cadmium (II) hexacyanoferrates are also suitable for the determination of caesium ions. The working range of the electrodes also depends on the conductivity of the solutions and can range from 10^-5 to 1 moll^-1. Typical standard deviations of the potential measurements are 3 mV.     

Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites</p> </p>

Summary Potassium nickel hexacyanoferrate, KNiFC, was incorporated in the porous matrix of zeolites by successive impregnation with Ni(NO₃)₂ and</o:p></p> K₄Fe (CN)₆.¹ CFC and PFC exchangers were first prepared by impregnating the potassium nickel hexacyanoferrate into the clinoptilolite and the synthetic P zeolite, respectively. Ion-exchange isotherms and breakthrough curves were plotted. Results showed that the CFC sorbent is suitable for removal of Cs⁺ where PFC is more suitable for Sr²⁺. Negative effect of Na⁺ as a competing ion in these exchangers was less than in the parent zeolites. Isotherm plots fitted the Langmuir equation.</p> </p>     

A study of vitamin A as a probe in critical micelle concentration determinations of surfactants

The effects of the heteroatom donor on the complexation of various metal ions by macrocyclic polyethers were qualitatively examined by application of the ligand exchange technique in a quadruple ion trap mass spectrometer. The metal ions, including K⁺, Cs⁺, Al⁺, Mg⁺, Cu⁺ and Ni⁺, were generated by laser desorption and allowed to react with 12-crown-4 and its nitrogen and sulfur analogs, cyclen and 1,4,7,10-tetrathiacyclododecane. The orders of gas-phase basicities were established as a comparison. The relative K⁺ and Cs⁺ binding affinities of 12-crown-4 are greatest, whereas cyclen has the highest binding affinity for all the other metal ions and also the highest gas-phase basicity.     

Distribution studies of metal ions on arsenophosphates of Sn(IV) and Cr(III) and on amine Sn(II) hexacyanoferrates (II) using radio tracers: Separation of Sr2+−Cs+, Hg2+−Ag+ and Hg2+−Zn2+

Summary Distribution studies of some metal ions have been made on Sn(IV) and Cr(III) arsenophosphates and on some samples of Sn(II) amine hexacyanoferrates(II), using radiotracers. The K_d values of Cs⁺ and Rb⁺ have been followed at varying HNO₃ concentrations also. As a result 3 useful binary separations have been achieved on Sn(IV) and Cr(III) arsenophosphates, such as Sr²⁺–Cs⁺, Hg²⁺–Ag⁺ and Hg²⁺–Zn²⁺.     

Physicochemical properties of alkali-metal exchanged type X zeolites

The changes in the physicochemical properties of a series of faujasite type X zeolites cation exchanged with K⁺, Rb⁺ and Cs⁺ have been studied by XRD, IR, thermoanalytical methods and sorption measurements. As a consequence of the enhanced scattering of X-rays by larger alkali metal cations, the percent relative intensity of the XRD peaks of cation exchanged zeolites was found to have decreased considerably. The framework IR spectra also showed analogous changes. The alkali metal exchange was found to enhance the thermal stability of the parent zeolite. The available void volume and specific surface area (obtained by low temperature nitrogen sorption) also decreased with the increase in the degree of exchange and cationic size. Equilibrium sorption capacities (298 K andP/P ₀=0.5) for water,n-hexane, cyclohexane and 1,3,5-trimethylbenzene also exhibited the same trend.NCL communication no. 6056.     

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.     

Isotopieeffekte bei der Bildung von Natriumkryptaten

The distribution of activity of²²Na⁺ and²⁴Na⁺ in the heterogeneous equilibrium of a cationic exchange resin and the aqueous or methanolic solution was measured in order to evaluate an isotope effect. Using Li⁺-charged ion exchanger in methanol, an enrichment of²⁴Na was observed. If bicyclic aminopolyethers (221, 222) are present in the solution, this effect is not seen. This means that the complexing agents above carry out an enrichment themselves, as could be shown by calculating the corresponding elementary separation factor. The enrichment of²⁴Na on the ion exchanger was measured directly by using Cs⁺-charged exchangers. The analytical method applied is described, and the limits of error are discussed.      

Investigation of the resistance of some naturally occurring and synthetic inorganic ion exchangers against gamma radiation

The effect of various doses of gamma radiation on the ion-exchange capacity, distribution coefficient values, elution behaviour, physical effect, pH titration and infrared spectra of some synthetic inorganic ion exchangers, namely the cerium substituted phosphates; and naturally occurring inorganic ion exchangers, zeolites from different parts of Iran, have been studied systematically.No significant change has been observed in the ion-exchange capacity (with the exception of CeP(Na), CeP(Di·Na) and zeolite 5 (deposits of arababad talas)), elution behaviour, physical effect, chemical stability and the infrared spectra of the synthetic ion exchangers irradiated upto a total dose of 200 kGy, while a change has been observed in the pH-titration and distribution behaviour. The increase in pH is sharper for irradiated samples with divalent cations than for the normal samples. Furthermore, the K_d values, and hence the selectivity towards certain cations increase with the total dose absorbed, reaching its optimum selectivity with the dose of 50–100 kGy. The natural zeolites chosen for these studies, show, similar pattern to those of synthetic ion exchangers, and in some cases an extremely high selectivity toward certain cations, like Be^II. These make, zeolites, which are naturally occurring ion exchangers more viable economically, and extremely useful alternative in this industry.     

Specific features of the absorption of divalent manganese ions from aqueous solutions by zeolites

Sorption properties of natural zeolites from various Russia’s deposits for the Mn²⁺ ion were studied in comparison with various industrial adsorbents and some minerals. It was demonstrated that the equilibrium sorption capacity of these materials can be raised by their Na⁺-modification. The natural zeolites are advantageous at low Mn²⁺ ion concentrations over synthetic cation exchangers and activated carbons. The sorption capacity of the natural zeolites grows with increasing temperature.     

A new ecomaterial zirconyl molybdopyrophosphate for the removal of 137Cs and 90Sr from HLLW

A new ecomaterial, zirconyl molybdopyrophosphate (ZMPP), was prepared by a coprecipitation method. The removal of Cs⁺ and Sr²⁺ ions from simulated strong acid HLLW using the ion exchange process on ZMPP had been investigated. It showed that there are more than 90% Cs⁺ and Sr²⁺ removed from the simulated HLLW on ZMPP despite the presence of other metal ions, such as Na⁺, Al³⁺, Fe³⁺, etc. in excess. Then ZMPP may likely be a selective ion exchanger for the removal of ¹³⁷Cs and ⁹⁰Sr directly from strong acid HLLW.     

Antimicrobial Properties of Zeolite-X and Zeolite-A Ion-Exchanged with Silver,Copper, and Zinc Against a Broad Range of Microorganisms

Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag⁺, Zn²⁺, and Cu²⁺ ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag⁺ ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag⁺, Zn²⁺, and Cu²⁺ ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.     

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.     

Strontium binding properties of inorganic adsorbents

A comparison of strontium sorption on synthetic inorganic ion exchangers and zeolites from 0.01M CaCl₂ solution, sea water and an artificial foodstuff fluid has been carried out in batch and column experiments. It was found that some adsorbents among the groups manganese dioxides, mixed titanium-manganese oxides, antimony-based materials and synthetic zeolites had the highest selectivity to strontium (K _d >1000). These adsorbents are interesting for further investigation concerning their use for radiostrontium decontamination of foodstuffs (if nontoxic), as well as for analytical purposes.     

Synthesis,structure, dehydration transformations and ion exchange characteristics of iron-silicate with various Si and Fe contents as mixed oxides

The synthesis of a new series of impregnated metal oxides with different Fe/Si ratios (0.5, 1 and 2) was obtained by the direct precipitation method. Physico-chemical properties and molecular formula of the obtained products were identified with different analytical techniques, such as chemical stability, XRD, IR, elemental and thermal analyses. Thermal kinetic parameters, such as order (n) and activation energy (E_a), of the solid-state phase transformations of the first dehydration process have been studied for the obtained materials from DTA thermograms. The ion exchange applications and the sorption properties of the materials with some radioactive nuclides have been studied, depending on the Fe/Si molar ratios. These investigations indicated that the ion exchange capacities as well as the selectivities of different materials towards the studied nuclides show the order Co²⁺ > Cs⁺ > Na⁺ at a certain pH.     

Assembly of ϵ-Keggin Polyoxometalate from Molecular Crystal to Zeolitic Octahedral Metal Oxide

Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. ³¹P NMR spectroscopy shows that reduction of Mo^VI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na⁺ is used as the adsorbent, which effectively separates C₂ hydrocarbon mixtures.     

Cation exchange properties of crown ether-phosphotungstic acid precipitates

Precipitate formation between phosphotungstic acid and crown ethers is a general phenomenon, producing solids with selective ion exchange behavior for the alkali metal ions. Distribution coefficients for Li⁺, Na⁺, K⁺, and Cs⁺ were measured for a series of these precipitates with different crown ethers. The sorption data are more complicated than for the corresponding phosphomolybdates and indicate a variability in the number of exchangeable sites with H⁺ and M⁺ concentration. The crown ether used markedly affects the cation selectivity of the phosphotungstate precipitates.