Hypothetical model structures for magadiite and sodium octosilicate, based on the structure of the zeolite dachiardite, are proposed that consist of layers of 6-member rings of tetrahedra and blocks containing 5-member rings attached to both sides of the layers. The infrared (IR) and nuclear magnetic resonance spectra of magadiite and sodium octosilicate have features in common with spectra of zeolites in the ZSM-5 and mordenite groups. A peak at 1225 cm-1 in the IR spectra of magadiite and sodium octosilicate is characteristic of zeolites containing 5-member rings, such as ZSM-5- and mordenite-type zeolites. The defect structures of pentasil zeolites may therefore be akin to layered alkali metal silicates containing zeolite-like domains, in which part of the silanol groups from adjacent silicate layers are condensed (cross-linked) forming siloxane linkages.

Cetyltrimethylammonium- and tetradecyltrimethylammonium-intercalated magadiites were prepared by direct syntheses, starting from sodium metasilicate (Na2O/SiO2 = 1.0) and nitric acid. Total substitution of sodium by cetyltrimethylammonium or tetradecyltrimethylammonium cations was not achieved in the range of surfactant: silicon molar ratios used in this study. When a phosphoniun-based surfactant replaces the ammonium surfactants in the same procedure, the result of the synthesis is a mixture of quartz and unmodified surfactant. If dodecylammonium bromide is used, an MCM-41 molecular sieve is obtained. The substitution of the silicon source by tetramethylammonium silicate or of nitric acid by hydrochloric, hydrofluoric, or acetic acids also yields MCM-41 molecular sieves, indicating that the formation of magadiite is greatly dependent on the presence of sodium cations and nitrate anions.

Silanol groups in protonated magadiite (H-magadiite) were characterized by 1H and 2H solid-state nuclear magnetic resonance (NMR). H-magadiite and deuterated (D) magadiite were synthesized by the treatment of Na-rich magadiite with 0.2 N HC1 and 0.2 N DC1, respectively. In the 1H NMR spectrum measured at room temperature, silanol groups of H-magadiite showed two signals at 3.75 and 5.70 ppm, indicating that two types of silanol groups were present. The ratio of silanol groups associated with strong hydrogen bonding (5.70 ppm) to those with weaker hydrogen bonding (3.75 ppm) was 2 to 1. The 2H NMR spectra of deuterated magadiite were measured in the temperature range from 150 to 440 K. In the spectra measured at temperatures below 294 K, silanol groups showed Pake doublet patterns. These patterns were composed of two components corresponding to the two types of silanol groups shown in the 1H NMR analysis. Both silanol groups produced wobbling motions with increasing temperature. Above 294 K, the profile of the Pake doublet pattern was transformed gradually to a near triangular pattern, indicating that the silanol groups underwent other motions also, such as a two-site jump.

New experimental data with respect to the solubility of natural and synthesized magadiite at elevated temperatures and in alkaline solutions are presented. The results show that the solubility of magadiite increases according to the expression ln(Kmag) = −8146·T(K)−1 − 5.71 from 20 to 100°C ($(\Delta G_{\text{R}}^0({\text{K}}_{\text{mag}})=19.6\pm 0.3$ and $\Delta H_{\text{R}}^0({\text{K}}_{\text{mag}})=16.2\pm 0.4\text{kcal}{\text{mol}}^{-1}$). The experimental results and the related data from the literature suggest that the formation of magadiite may be favored by a decrease of temperature and pH (pH >9) as well by large amounts of Na+ ions and low ionic strength. These effects are related to the value of $\Delta H_{\text{R}}^0({\text{K}}_{\text{mag}})$, the distribution of dissolved silica species, the stoichiometry of magadiite, and the occurrence of negatively-charged species, respectively.

Human health problems are often related to contamination of the aqueous environment by toxic metal ions. In the present study, two layered alkali silicates (magadiite and octosilicate) were examined to assess removal of Pb2+ from aqueous solutions in terms of quantity and kinetics. The ion-exchange reaction between the silicates and aqueous solutions of lead(II) acetate at various concentrations was examined at room temperature for 24 h. The adsorption isotherms were H-type, showing the strong interactions between Pb2+ and the silicates. The amounts of Pb2+ adsorbed were as much as 1.23 mmol Pb/g magadiite and 2.32 mmol Pb/g octosilicate, which are larger than the reported values for various ion exchangers. They were larger than the theoretical cation exchange capacities (2.2 and 3.7 meq/g for magadiite and octosilicate, respectively), suggesting that the collection of Pb2+ included the precipitation as basic lead salts in addition to the ion exchange. The adsorption isotherms for magadiite and octosilicate fitted the Langmuir equation with correlation coefficients, R2, of 0.9991 and 0.9972, respectively. The adsorption of Pb2+ onto the layered alkali silicates from acidic aqueous solution was examined to obtain smaller amounts of adsorbed Pb2+ (0.32 mmol Pb/g magadiite and 0.34 mmol Pb/g octosilicate), confirming the important role of pH on the surface charge of the layered silicates in terms of ion exchange. The adsorption of Pb2+ reached equilibrium within 5 min for magadiite while it took 60 min for octosilicate. The difference was in the particle morphology; smoother diffusion of Pb2+ was possible through flower-shaped aggregates of particles of magadiite.

The intercalation of europium ions (Eu3+) into the interlayer space of a layered silicate, magadiite, was conducted by ion-exchange reactions between magadiite and europium(III) chloride. X-ray diffraction and elemental analysis results indicated that Eu3+ cations were intercalated into the interlayer space of magadiite. The ion exchange between Eu3+ and Na+ occurred preferentially so that the adsorbed Eu3+ amounts were controlled quantitatively. Thermal transformation of the original layered structure was suppressed by the intercalation of Eu3+. The resulting intercalation compounds exhibited photoluminescence arising from the intercalated Eu3+. The luminescence intensity varied in accordance with the amount of Eu3+ absorbed, suggesting that the self-quenching occurred at higher loading levels. The luminescence intensity was also changed by the heat treatment, corresponding to the change in the surroundings of the Eu3+ adsorbed, induced by the removal of the adsorbed water molecules and the hydroxyl groups of the silicate.

The contamination of aquatic environments by toxic metals such as radionuclides is of great concern because of the tendency of those metals to accumulate in the vital organs of humans and animals, causing severe health problems. The objective of this study was to investigate the use of natural and modified magadiite clay as an adsorbent to remove Th(IV), U(VI), and Eu(III) from aqueous solutions. Magadiite from the Amazon region, Brazil, was modified chemically with 5-mercapto-1-methyltetrazole (MTTZ) using a multi-step or heterogeneous synthesis pathway. The natural and modified materials were characterized using 29Si and 13C nuclear magnetic resonance, scanning electron microscopy, nitrogen gas adsorption, and elemental analysis. The physical-chemical properties of the chemically modified magadiite sample were modified, e.g. the specific surface area changed from 35.0 to 678.9 m2 g−1. The ability of the magadiite to remove Th(IV), U(VI), and Eu(III) from aqueous solution was then tested by a series of adsorption isotherms adjusted to a Sips equation. The effects of properties such as pH, contact time, and metal concentration on the adsorption capacity were studied. The adsorption maxima were determined to be 7.5 × 10−3, 9.8 × 10−3, and 12.9 × 10−3 mmol g−1 for Th(IV), U(VI), and Eu(III), respectively. From calorimetric determinations, the quantitative thermal effects for all these cations/basic center interactions gave exothermic enthalpy, negative Gibbs free energy, and positive entropy, confirming the energetically favorable conditions of such interactions at the solid/liquid interface for all systems.

Hydrothermal syntheses of a silicate structure comprising a single tetrahedral layer, known as ilerite, were conducted in the presence of tin (SnCl4·5H2O) as a heteroatom. The main aim of the study was to investigate the influence of the above-mentioned compound on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms. For comparison, unmodified ilerite, ilerite impregnated by SnO2, and ilerite synthesized in the presence of Al (aluminum isopropoxide) were also used. The ilerite structure observed was that of Na-ilerite. Syntheses of samples with various Sn/Si ratios (up to the value of 0.01Sn/4Si) and Al/Si ratios (up to the value of 0.005Al/4Si) resulted in a magadiite structure. Synthesis methods applied to Sn-modified materials were found to be unsuitable for the introduction of tetrahedrally substituted Al. The characterization methods used were X-ray diffraction (XRD), temperature-programmed reduction (TPR), and diffuse reflectance infrared fourier transform (DRIFT) spectroscopy. and these indicated the presence of metal oxide species on the surfaces of the crystals, in addition to a small degree of replacement of Si by Sn or Al in the tetrahedral layers.

Somen-alkyldiamines with thegeneral formulae H2N(CH2)nNH2 (n = 2–5) were intercalated into the layered silicic acid magadiite, from aqueous solution, causing an increase in the original interlayer distance of 1172 pm. The synthetic magadiite and all intercalated compounds were characterized by elemental analysis, infrared vibrational spectroscopy, X-ray diffractometry, 29Si nuclear magnetic resonance in the solid state, thermogravimetry, scanning electron microscopy, surface area and porosity. The intercalation was followed through a batch-wise method at 298±1 K and gave the maximum amounts 3.70, 2.80, 1.75 and 1.18 mmol g−1, for n varying from 2 to 5, respectively. The well characterized magadiite was calorimetrically titrated in a heterogeneous medium, to obtain the thermodynamic data of intercalation at the solid/liquid interface. Linear correlations were obtained for the number of moles intercalated (Nf), th einterlamellar distance (d) and the specific enthalpy (Δinth) values of the interactive process as a function of the number of C atoms of the aliphatic organic chains (nC) for n-alkyldiamine: Nf = (5.36±0.25) − (0.86±0.07)nC, d = (1406.6±1.9) + (20.9±0.5)nC and Δinth = (5.96±0.25) + (0.06±0.01)nC. The basic N guest atom/silanol acidic center interactions inside the host nanospace gallery gave exothermic enthalpies, positive entropies and negative Gibbs free energy values. This set of data suggests the spontaneity of these intercalation reactions.

In order to extend the application of magadiite to optical fields (rather than the usual focus on adsorption, catalysis, ion exchange, etc.), a magadiite-CdS (Mag-CdS) composite was synthesized from Na-magadiite by ion exchange. Various techniques were used to characterize the composite. X-ray diffraction results indicated that the Mag-CdS composite retained the host magadiite structure in spite of decrease in the intensity of the X-ray diffraction peak of the host magadiite. The analytical results confirmed the formation of the Mag-CdS composite, along with the modification of the optical properties of CdS by the host magadiite.

Hydrothermal syntheses of the magadiite, a layered silicate structure, were conducted in the presence of a heteroatom source (SnCl4.5H2O) with the intention of investigating its influence on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms in the abovementioned structure. For comparison, unmodified magadiite, Al-containing magadiite, and impregnated magadiite were synthesized. The magadiite structure was identified for samples with Sn/Si ratios up to 0.015. Synthetic methods applied to Sn-modified materials were found to be unsuitable for the introduction of Al. The characterization methods used were X-ray diffraction, temperature-programmed reduction, and 29Si magic angle spinning nuclear magnetic resonance and these revealed the substitution of Si by Sn in the silica layers. No additional acid centers on the surfaces of the modified samples were detected, suggesting the presence of the desired four-coordinate Sn in the silica layers.

Intercalation of an ammonium amphiphile having an azobenzene chromophore, 4-dodecyloxy-4 ‘-(trimethylammoniopentyloxy)azobenzene and 4-(ω-trimethylammoniodecyloxy) -p’- (octyloxy)azobenzene bromide, into the layered silicate magadiite (ideal formula Na2Si14O29·nH2O) was carried out by a conventional ion exchange reaction in an aqueous medium. An intercalation compound with the ideal formula {(C12AzoC5N+)1.4H0.6·Si14O29·nH2O} was obtained. Based on the change in the basal spacing (to 4.21 nm) after the reaction and the visible absorption spectrum of the product, the intercalated azo dyes appear to form a J-aggregate in the interlayer space of magadiite. Under UV and visible light irradiation, the intercalated azo chromophore exhibited reversible transcis isomerization in the interlayer space of magadiite. This is the first successful report of photochemical reactions of guest species in the interlayer space of magadiite.

Composites based on ZnS nanparticles embedded in layered magadiite were synthesized via a three step process : protonation of Na-magadiite, ion exchange in order to introduce Zn(NH3)42+ in the interlayer space, and addition of Na2S to form ZnS particles in the interlayer space of magadiite. The composites obtained were characterized by X-ray power diffraction (XRD), Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS), Transmission Electron Microscopy (TEM), Raman spectroscopy, Photoluminscence spectra (PL), and UV-visible transmission spectra (UV-vis). Results indicated that ZnS nanoparticles embedded in magadiite presented different optical properties and photoluminescence enhancement properties compared with those of uncovered ZnS particles (without host magadiite).

The surface properties of various synthetic layered silicates, Na-kanemite, Nakenyaite and magadiite, exchanged with H, K and Ca, were examined using high-resolution nitrogen and argon adsorption and the data were treated using the Derivative Isotherm Summation method. Using argon as an adsorbate, the aspect ratio of platelets can be determined. In the case of magadiite exchanged with various cations, the stacking of particles is influenced by the nature of the exchangeable cations, thicker platelets being observed for ions with low polarizability. Highresolution argon adsorption data also confirm some structural information previously deduced from Raman spectroscopy experiments concerning the existence of rather open six-membered rings at the surfaces of both magadiite and kenyaite. Furthermore, in the low-energy domain of the isotherms, argon forms a very organized film on basal planes, suggesting a commensurate relationship between silica framework and argon atoms for both magadiite and kenyaite, contrary to what is observed for kanemite. Nitrogen adsorption results reveal the presence of polar sites on the surface of all the investigated minerals but does not allow us to propose an unequivocal assignment for such sites.

Syntheses of Na-magadiite were performed under hydrothermal conditions in a water/alcohol medium. It is only possible to obtain a pure and well crystallized magadiite sample using a water/ethanol medium at a water/ethanol molar ratio of ∼0.12. As shown by thermal analysis and 1H liquid nuclear magnetic resonance spectroscopy, ethanol is not incorporated into the magadiite. Intercalation of dodecyl- and hexadecyltrimethylammonium cations in the interlayer space of Na-magadiite at different theoretical ion-exchange rates shows that the experimental ion-exchange rates are in good agreement with the theoretical ones. However, scanning electron micrographs of the sample having a theoretical ion exchange rate of 25–75% shows that the exchanges are not homogeneous (both thin and thick platelets are present). Attempts to obtain a Si-pillared compound starting from C16TMA-magadiite as the host material leads to a microporous compound having a BET surface area of 778 m2g-1.

The intercalation of Tb(III) into layered magadiite is achieved by three-step ion exchanges with H+/Na+, TBA+ (tetra-n-butylammonium ions)/H+ and Tb(EDTA)3+/TBA+. Various techniques, including powder X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), thermogravimetric and differential thermogravimetry (TG-DTG), Fourier transform infrared (FTIR) spectroscopy, and photoluminescent spectroscopy (PL), were employed to characterize the Tb-intercalated magadiites. The XRD results revealed that the basal spacing of the Tb-intercalated magadiites was obviously larger than that of the Na-magadiite, confirming the intercalation. The IR spectra showed no bands attributable to EDTA in the Tb-intercalated magadiites, indicating that the EDTA has broken away from Tb(III)-ETDA complexes during ion exchange. Moreover, the basal spacing of Tb-intercalated magadiite tends to increase slightly with the increase in water content in the Tb-intercalated magadiite. The PL spectra show weak emissions, attributed to 5D4-7FJ (J = 3, 4, 5, 6) transitions of Tb3+.

A synthetic protonic magadiite was used as a silica source to prepare zeolitic material (PLS-1) in the presence of tetramethylammonium hydroxide and water. The conversion of the protonic magadiite to the PLS-1 phase was achieved at 150°C after 5 days, or at 170°C after 3 days for SiO2: TMAOH:H2O molar ratios of 2.54:1:4.4. The synthesis of the pure PLS-1 phase depended also on the amounts of tetramethylammonium hydroxide and water used. Analysis by 29Si magic angle spinning nuclear magnetic resonance spectroscopy confirmed the layered character of the PLS-1 phase with a resonance at −93 ppm, and its dehydroxylation-condensation process. The chemical formula of (TMA)2Si18O33(OH)6 for PLS-1 was refined with the Rietveld method and the tetrahedron-splitting model. The later model has been proposed to describe the presence of silanol defects in the layered structure of PLS-1. Upon calcinations of the PLS-1 phase at temperatures >400°C, the removal of TMA cations and dehydroxlyation of PLS-1 layers resulted in a three-dimensional structure phase identified as the CDS-1 phase, with a chemical formula of Si18O36. The CDS-1 phase exhibited a large specific surface area of 288 m2/g and microporous character, as indicated by the nitrogen adsorption isotherms. The temperature-programmed desorption profile of ammonia indicated that CDS-1 exhibited one weak type of acid sites, confirmed, by pyridine desorption studies, as weak Lewis acid sites.