Study of Ion-Exchanged Microporous Lithosilicate Na-RUB-29 Using Synchrotron X-Ray Single-Crystal Diffraction and Li MAS NMR Spectroscopy

Synchrotron X-ray single-crystal diffraction analyses revealed that as-synthesized and Na-exchanged RUB-29 (Cs_1−x, Na_x)₁₄Li₂₄[Si₇₂Li₁₈O₁₇₂]·yH₂O (x=0, 0.9) displays the lattice symmetry I222. With increasing ion-exchange time, the Na cations preferentially replace Cs in the larger sites located at the intersections of the 10MR/10MR/8MR channels. The smaller Cs sites are then replaced. While Na cations are easily incorporated on the Cs sites, most of non-framework Li cations remain in the channel system. Relocation of Li cations onto new sites within the channels was observed only after 13 days of ion exchange. Using high-field (14.1 T) NMR spectroscopy, at least six separate ⁶Li resonances could be resolved for the first time by solid-state ⁶Li MAS NMR spectroscopy and assigned to Li in the framework and non-framework sites of the microporous lithosilicate materials. The fate of Li in both framework and extra-framework sites during exchange was also followed by ⁶Li MAS NMR spectroscopy with an Na-exchanged RUB-29 powder sample.     

Laws and mechanism of adsorption of cations by different ion-exchange forms of silica gel

Using radioactive tracer method, the regularities of adsorption of over 30 mono-, di- and trivalent cations including transition metal and lanthanide ions on the H, Ca- and Al-forms of silica gel are established. It has been shown that the affinity of cations of the same charge to the silica gel surface depends both on the nature of the adsorbing ion and the nature of exchangeable cation on the surface. Adsorption of alkali earth metal ions on the Ca-form of silica gel increases with a decrease of their radius i.e. an inversion of the sequence of adsorption compared to H- or Al-form of this adsorbent or polymeric cation-exchange resins takes place. For lanthanide ions the sequence of adsorption is the same for all ion-exchange forms of the silica gel studied, namely, an increase of adsorption with a decrease of their crystallographic radius, i.e. from La ³⁺ to Lu ³⁺ takes place. The laws observed are explained by taking into account the fact that adsorption of cations by silica gel is determined by both electrostatic interactions and additional covalent/donor–acceptor interactions between the surface and cations. The latter is due to formation of π-bonds between the electron pair in surface oxygen and vacant p-, d- or f-orbital of adsorbing cations.     

Studies on Natural CXN Zeolite： Modification, Framework De-alumination and Ion-exchange

A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with NH4^ exchange by using ammonium salt and calcinations (procedure Ⅰ), or with NH4 exchange followed by treatment with acid (procedure Ⅱ). The coordination state of Si and A1 atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD,EDX,^29Si and ^27Al MAS NMR, Ag^ ion exchange and Ne adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and A1 atoms,the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure Ⅱ possesses high ion exchange capacity, open and perfect pore system, and high thermal stability.     

First-row transition metal atoms adsorption on rutile TiO2(110) surface

We performed periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO₂(110) surface (at low coverage, ???=?1/3) to investigate the interaction of an individual metal atom with TiO₂ and to compare it with a study previously done on MgO(100). We considered partial period of Mendeleev??s table from K to Zn. The overall evolution of the adsorption energies shows two maxima as for MgO(100). Two main differences, however, exist: the adsorption energy is much stronger and the first maximum is enhanced relative to the second one. This is attributed to the reducibility of the surface titanium cation. When the adsorbed metal is electropositive, it is oxidized under adsorption transferring electrons to titanium cations. We present the effect of introducing a Hubbard term to the gradient-corrected approximation band-structure Hamiltonian (GGA?+?U). The introduction of a reasonable Hubbard correction preserves the trends and allows localizing the electron of the reduction on Ti atoms in the near surface region. Finally, our results conclude that for heavier M atoms of the period, insertion is energetically favored relative to adsorption.     

Thermodynamics and kinetics of adsorption of Cu(II) from aqueous solutions onto multi-walled carbon nanotubes

Release of heavy metals into water as a result of industrial activities may pose a serious threat to the environment. The objective of this study is to assess the uptake of Cu²⁺ from aqueous solutions onto multi-walled carbon nanotubes (MWCNT). The potential of the t-MWCNT to remove Cu²⁺ cations from aqueous solutions was investigated in batch reactor under different experimental conditions. The processing parameters such as initial concentration of Cu²⁺ ions, temperature, and adsorbent mass were also investigated. Copper uptake was quantitatively evaluated using the Langmuir, Freundlich and Dubinin–Kaganer–Radushkevich (DKR) models. In addition, the adsorption equilibrium was described well by the Langmuir isotherm model with maximum adsorption capacity of 12.34 mg/g of Cu²⁺ cations on t-MWCNT. Various thermodynamic parameters, such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated. The thermodynamics of Cu²⁺ cations adsorption onto t-MWCNT system pointed at spontaneous and endothermic nature of the process. Using the second-order kinetic constants, the activation energy of adsorption (E_a) was determined as 27.187 kJ/mol according to the Arrhenius equation.     

Adsorption of CO2 and N2 in Na–ZSM-5: effects of Na+ and Al content studied by Grand Canonical Monte Carlo simulations and experiments

Zeolite crystals with cations present, such as ZSM-5, are widely used for gas sequestration, separations, and catalysis. One possible application is as an adsorbent to separate CO₂ from N₂ in flue gas mixtures. Typically, the zeolite framework is of a SiO₂ composition, but tetravalent Si atoms can be replaced with trivalent Al atoms. This change in valence creates a charge deficit, requiring cations to maintain the charge balance. Experimental studies have demonstrated that cations enhance adsorption of polar molecules due to strong electrostatic interactions. While numerous adsorption studies have been performed for silicalite-1, the all-silica form of ZSM-5, fewer studies on ZSM-5 have been performed. Grand Canonical Monte Carlo simulations were used to study adsorption of CO₂ and N₂ in Na–ZSM-5 at T = 308 K, which is ZSM-5 with Na⁺ counter-ions present. The simulations suggest that a lower Si/Al ratio (or higher Na⁺ and Al content) substantially increases adsorption at low pressures. At high pressures, however, the effect of the Al substitutions is minor, because the Al^?/Na⁺ sites are saturated with guest molecules. Similarly, a lower Si/Al ratio also increases the isosteric heat of adsorption at low loading, but the isosteric heats approach the silicalite-1 reference values at higher loadings. Comparison of simulations and experimental measurements of the adsorption isotherms and isosteric heats points to the importance of carefully considering the role of charge on the Na⁺ cations, and suggest that the balancing cations in ZSM-5, here Na⁺, only have partial charges.     

Adsorption of trace elements or radionuclides on hydrous iron oxides

Factors that influence the adsorption of trace elements or radionuclides on hydrous iron oxides were investigated. The adsorption of monovalent cations (Cs⁺, Rb⁺) on hydrous iron oxides is not strongly pH-dependent and it can be regarded as nonspecific. On the other hand, the adsorption of Ag⁺, divalent cations (Zn²⁺, Cd²⁺, Mn²⁺, Sr²⁺) or trivalent cations (Cr³⁺, La³⁺, Ce³⁺, Eu³⁺, Gd³⁺, Er³⁺, Yb³⁺) is strongly pH-dependent. The regularities of the adsorption of these cations on hydrous iron oxides are discussed. Also, the differences in the adsorption behaviour of some divalent and trivalent cations are explained. Freshly precipitated iron(III) hydroxide can be used for the decontamination of radionuclides from low-level waste solutions. However, the efficacy of decontamination depends on the oxidation state and the chemical properties of radionuclides.     

The effect of the dehydration conditions of chitosan-based polymeric adsorbents on the adsorption of nickel cations

The structure and adsorption properties (with respect to water vapor and nickel cations) of chitosan samples dehydrated by either lyophilization after precipitation with NaOH or Na₂CO₃ or drying in air are investigated. IR spectroscopy and X-ray diffraction data testify that the lyophilization causes both changes in the conformation of chitosan macromolecules and a substantial rise in the crystallinity of the polymer to compare with the air dried one. Chitosan structure ordering resultant from the lyophilization noticeably increases its sorption ability with respect to both water vapor and nickel cations. For example, the sorption capacity of the lyophilized chitosan with respect to nickel cations is as high as 4.5 mmol/g and, thus, is threefold higher than that of air-dried chitosan. The comparative analysis of water adsorption isotherms in the region of low degrees of filling indicates that chitosan structure ordering resultant from the lyophilization changes the number and the energy of primary adsorption sites.     

Adsorption of small molecules on silver clusters

We report investigations of adsorption of N(2) and O(2) molecules on silver cluster cations. We have first revisited structures of small silver clusters based on first-principles calculations within the framework of density functional theory with hybrid functional. The 2D to 3D transition for the neutral clusters occurs from n = 6 to 7 and for cations, in agreement with experiments, from n = 4 to 5. With the refined structures, adsorption energies of N(2) and O(2) molecules have been calculated. We have identified characteristic drops in the adsorption energies of N(2) that further link our calculations and experiments, and confirm the reported 2D-3D transition for cations. We have found that perturbations caused by physisorbed molecules are small enough that the structures of most Ag clusters remain unchanged, even though physisorption stabilizes the 3D Ag(7)(+) structure slightly more than the 2D counterpart. Results for pure O(2) adsorption indicate that charge transfer from Ag(n)(+) to O(2) occurs when n > 3. Below that size oxygen essentially physisorbes such as nitrogen to the cluster. We interpret the experimentally observed mutually cooperative co-adsorption of oxygen and nitrogen using results from density functional theory with generalized gradient approximations. The key to the enhancement is N(2)-induced increase in charge transfer from Ag(n)(+) cations to O(2).     

Effect of the alkyl chain length on micelle formation for bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides

Dimeric alkylammonium salts – gemini surfactants – due to their unusual very low critical micelle concentration and minimal inhibitory concentration are subject to intensive research as surface active and antimicrobial compounds. Thanks to the presence of two positively charged nitrogen atoms and a large molecular surface, gemini surfactants are also very efficient corrosion inhibitors. To strengthen the electrostatic adsorption of ammonium cations on a metal surface, which is a key parameter in the inhibition of corrosion, heteroatoms (O, S, N, or P) and π-electron systems can be introduced into the gemini surfactant structure to increase chemical adsorption. In this study, we investigated the relationship between the alkyl chain length and critical micelle concentration for gemini surfactants containing an oxygen atom in the spacer, that is, bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides, for potential use as corrosion inhibitors.     

Removal of divalent nickel cations from aqueous solution by multi-walled carbon nano tubes: equilibrium and kinetic processes

Release of heavy metals into water as a result of industrial activity may pose a serious threat to the environment. In this study, the potential of multi-walled carbon nano tubes (MWCNT) to remove Ni²⁺ cations from aqueous solutions was investigated in a batch reactor under different experimental conditions. The effects on the removal process of conditions such as initial concentration of Ni²⁺ ions, temperature, and adsorbent mass were investigated. Nickel uptake was quantitatively evaluated by use of the Langmuir, Freundlich, and Dubinin?CKaganer?CRadushkevich isotherm models. For 20?mg/L initial Ni²⁺ cation concentration, adsorption capacity increased from 8.12 to 11.75?mg/g when the temperature was increased from 25 to 65?°C, an indication of the endothermic nature of adsorption process. In addition, the adsorption equilibrium was well described by the Langmuir isotherm model; maximum adsorption capacity was 17.86?mg/g Ni²⁺ cations on HNO₃-treated MWCNT (t-MWCNT). The results obtained in this study show that adsorption of Ni²⁺ on t-MWCNT is a spontaneous and endothermic process. By use of second-order kinetic constants and the Arrhenius equation, the activation energy of adsorption (E _a) was determined as 5.56?kJ?mol^?1.     

Participation of electrolyte cations in albumin adsorption onto negatively charged polymer latices

The participation of electrolyte cations in the adsorption of bovine serum albumin (BSA) onto polymer latices was investigated. The latices used were hydrophobic polystyrene (PS), and hydrophilic copolymers, i.e., styrene (St)/2-hydroxyethyl methacrylate(HEMA) copolymer [P(St/HEMA)] and styrene/acrylamide (AAm) copolymer [P(St/AAm)]. Three kinds of electrolyte cations (Na⁺, Ca²⁺, Mg²⁺) were used as the chloride. The amount of BSA adsorbed in every cation medium showed a maximum near the isoelectric point (iep, pH about 5) of the protein. The amounts of BSA adsorbed onto copolymer latices (except in the acidic pH region lower than the iep) were considerably smaller than that onto PS latex because of the steric repulsion and the decrease in the hydrophobic interaction between BSA and copolymer latices. In the acidic pH region, there was little difference in the amount of BSA adsorbed in every cation medium. However, in the pH region higher than the iep, the amounts of BSA adsorbed (particularly onto PS latex) in divalent cations (Ca²⁺ and Mg²⁺) media were relatively greater compared with that in a monovalent (Na⁺) one. This result was interpreted on the basis of the differences in such effects of electrolyte cations as dehydration power, suppression of the electrostatic repulsion, and binding affinity to BSA molecule. Ion Chromatographic estimation of the amounts of electrolyte cations captured upon BSA adsorption (in pH > 5) revealed that divalent cations were incorporated into the contact interface between the latex and BSA molecule so as to prevent the accumulation of anion charge and facilitate the protein adsorption.     

Adsorption phenomena in the systems containing macrocyclic cavitand cucurbit [7]uryl

Adsorption phenomena at the mercury electrode/cucurbit[7]uryl aqueous solutions are studied by the measuring of the electrode differential capacitance C as a function of potential E. The data obtained showed that the adsorption potential region is abnormally wide (>2 V). Two segments are observed in the C,E-dependences, which relate to adsorption layers with different structure. The complicated adsorption layers forming in the studied systems can be explained by the structure of the cucurbit[7]uryl cavitand whose complexes with inorganic cations are formed by the cation binding by oxygen-containing groups of external portals, rather than their inclusion into the cavitand’s inner cavity as in the case of cryptate formation. Adsorption parameters for adsorbate layers formed in the cucurbit[7]uryl + Na₂SO₄ solution are calculated. The data obtained evidence a rather strong potential dependence of the properties of the adsorption layers formed at the electrode/solution interface in the studied system.     

Use of poly(N,N-dimethylacrylamide-co-sodium acrylate) hydrogel to extract cationic dyes and metals from water

Poly(N,N-dimethylacrylamide-co-sodium acrylate) hydrogel, which bears negatively charged –COO⁻ groups was used to extract organic or inorganic solutes from water. Some model dyes and metal ions have been studied. Cationic dyes are strongly adsorbed and retained by the polymer while adsorbance of hydrophobic dyes was very low and that of anionic dyes was negligible. Both maximum adsorption and equilibrium binding constant varied from one cationic species to the other depending on the chemical structure of the dye, the presence of functional chemical groups and the hydrophobic–hydrophilic balance. In the case of metal cations, adsorption depended on valence. The hydrogel can be regenerated in an aqueous phase of low pH and thus be reused in several adsorption procedures.     

Weak specific adsorption of ions

It is shown that the weak specific adsorption of ions not involving the recharging of the electrode surface is characterized by the following unusual features: practical absence of any shift of p.z.c.; a very small discrepancy between the experimental differential capacity curves and similar curves calculated under the assumption that specific adsorption is absent (q₁ = 0); insensitivity of the total surface excess of cations to their distribution between the dense and diffuse layers; practical independence of q₁ of temperature and the bulk concentration of binary electrolyte; practical coincidence of c.t.p. calculated for different concentrations of surface-active supporting electrolyte assuming q₁ = 0. It is also shown on the basis of the experimental data for the system {mc CsCl + (1 ? m)c LiCl} that the main fraction of the effective charge, determined by the mixed electrolyte method of Hurwitz—Parsons, results from the true specific adsorption of Cs⁺ cations at the Hg/H₂O interface and only a small fraction of this charge (?20%) can be associated with different positions of the o.H.p. for Li⁺ and Cs⁺ ions.     

Mechanisms of Tebuconazole Adsorption in Profiles of Mineral Soils

The study attempted to identify the soil components and the principal adsorption mechanisms that bind tebuconazole in mineral soils. The K_F values of the Freundlich isotherm determined in 18 soils from six soil profiles in batch experiments after 96 h of shaking ranged from 1.11 to 16.85 μg^1−1/n (mL)^1/n g⁻¹, and the exponent 1/n values from 0.74 to 1.04. The adsorption of tebuconazole was inversely correlated with the soil pH. Both neutral and protonated forms of this organic base were adsorbed mainly on the fraction of humins. The adsorption of the protonated form increased in the presence of hydrogen cations adsorbed in the soil sorption sites. Fourier transform infrared spectroscopy coupled with the molecular modeling studies and partial least squares regression analysis indicated that the tebuconazole molecule is bound in the organic matter through the formation of hydrogen bonds as well as hydrophobic and π–π interactions. Ion exchange was one of the adsorption mechanisms of the protonated form of this fungicide. The created mathematical model, assuming that both forms of tebuconazole are adsorbed on the organic matter and adsorption of the protonated form is affected by the potential acidity, described its adsorption in soils well.     

Effect of the Nature of Organic Templates and Alkali Metal Cations on the Phase Composition and Adsorption Properties of Novel High-Silica Zeolites IPC-1 And IPC-2

We have obtained novel high-silica zeolites IPC-1 and IPC-2 and we have determined the effect of the nature and concentration of organic templates, including specially synthesized templates, and alkali metal cations as well as other factors on their phase composition and adsorption properties. We have noted that a decisive role is played by the balance between the structure-directing effects of the templates and the cations. Using temperature programmed desorption of ammonia (TPDA) and temperature- programmed cumene cracking, we have determined that strong acid sites are present in IPC-1 and IPC-2 zeolites. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 236–241, July–August, 2005.     

Characterization of short-time dealumined HZSM-5 zeolites

Temperature-programmed desorption (TPD) of water was applied to characterize short-time dealuminated HZSM-5 zeolites. Using a regularization method, distribution functions of the effective desorption energy of water were calculated. The results clearly show that during dealumination a new adsorption site is formed which can be attributed to non-framework or transient aluminium species. The highest concentration of these sites was observed for a dealumination time of 25-30 min. NO adsorption studies support this result. Furthermore, it could be concluded that the heterogeneity and the average acid strength of the remaining Si-OH-Al groups of the dealuminated samples do not change compared to the Si-OH-Al groups of the parent HZSM-5 zeolite. This revised version was published online in July 2006 with corrections to the Cover Date.