Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.     

8-Hydroxyquinoline intercalated montmorillonite composite: characterization and application for copper ion determination as potentiometric electrode

Journal of Solid State Electrochemistry - The intercalation of 8-hydroxyquinoline (HQ) organic chelating ligand onto the structure of Na+-montmorillonite (MMT) was prepared and investigated by...     

Infrared study of HDTMA+ intercalated montmorillonite

In this paper, FTIR spectroscopy using attenuated total reflection (ATR) and KBr pressed disk techniques has been used to characterize sorbed water and HDTMA+ in organo-clay. Sorbed water content decreases with the intercalation of HDTMA+. With the decrease of the sorbed water content, the position of the nu2 mode shifts to higher frequency dramatically while the stretching vibration shifts to lower frequency slightly, indicating that H2O is less strongly hydrogen bonded. This might be resulted from the polarization of H2O molecules by the changeable cations and HDTMA+. FTIR spectra show that both antisymmetric and symmetric CH2 stretching absorption bands shift to low frequencies with increase of amine concentration within the galleries of montmorillonite, elucidating the increase of ordered conformation. Furthermore, the present study demonstrates that the antisymmetric CH2 stretching mode is more sensitive to the conformational ordering than the symmetric stretching mode. When KBr pressed disk technique used, two well resolved absorption bands at 730 and 720 cm(-1), and at 1473 and 1463 cm(-1), corresponding to the methylene scissoring and rocking modes, respectively, could be observed in FTIR spectra of organo-clays with relative higher concentration of surfactant. However, the FTIR spectra using ATR technique only display singlets and they are independent of amine concentration and chain conformation. Our present study demonstrates that FTIR spectroscopy using KBr pressed disk technique is more suitable to probe the conformational ordering of surfactant in organo-clays than that suing ATR technique does.     

New layered double hydroxides containing intercalated manganese oxide species: synthesis and characterization

Manganese oxide species (MnO(x)) have been intercalated within the gallery spaces of Mg-Al layered double hydroxides (LDHs). Synthesis of these materials was achieved by ion-exchange of the LDH-nitrate precursor with permanganate anion followed by reduction with organic reagents, such as glucose, ethanol, and ascorbic acid. Elemental analysis, X-ray diffraction, FT-IR spectroscopy, Raman spectroscopy, HR-TEM, and N(2) sorption analyses have been used to characterize these materials. TEM micrographs of LDH-MnO(x) materials revealed platelike morphology, characteristic of hydrotalcite-like compounds. Chemical analysis results showed that permanganate anions exchanged with nitrate anions. FT-IR and Raman spectroscopy confirmed the reduction of the permanganate anions after treatment with the organic reagents. The XRD diffraction patterns of LDH-MnO(x) revealed that the layer structure is maintained after all synthetic steps. The observed basal spacings of intercalates varied depending on the reducing agent; the largest expansion was 9.93A, corresponding to the use of ascorbic acid. The specific surface areas were also affected according to the organic reagent used, indicating that the structural modifications in the interlayer domain observed by X-ray diffraction also influence the microtextural properties.     

Synthesis of an intercalated compound of montmorillonite and 6-polyamide

Natural montmorillonite, fractionated from bentonite produced in Yamagata, Japan, was ion-exchanged for NH ₃ ⁺ –(CH₂)₁₁–COOH, NH ₃ ⁺ –(CH₂)₅–COOH, Al³⁺, Cu²⁺, Mg²⁺, Co²⁺, Li⁺, K⁺ and H⁺. The mixtures of the ion-exchanged montmorillonite and -caprolactam were heated at 263°C in glass ampoules for various periods. The intercalated compounds before and after the heating were examined by X-ray powder diffraction, DSC and GPC. Although -caprolactam was not polymerized without montmorillonite, it was polymerized at 263°C in the presence of montmorillonite. The polymerization rate varied with the interlayer cations in the order of NH ₃ ⁺ –(CH₂)₁₁–COOH>Al³⁺>NH ₃ ⁺ –(CH₂)₅–COOH>H⁺>Cu²⁺>Mg²⁺>Co²⁺>Li⁺>K⁺. After heating at 263°C for 5 h, the mean number-average molecular weight was about 1.5×10⁴. Although the interlayer distance of NH ₃ ⁺ –(CH₂)₁₁–COOH type montmorillonite/-caprolactam compound increased from 2.85 nm to 4.90 nm by heating at temperatures above the melting point of -caprolactam, those of other compounds were not changed. After heating at 263°C, an intercalated compound of montmorillonite and 6-polyamide, whose interlayer distance was more than 10 nm, was obtained. It is concluded that montmorillonite acts as a Brönsted acid and initiates the open ring polymerization of -caprolactam and that the driving force of swelling is the polymerization energy.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Theoretical and experimental study of montmorillonite intercalated with tetramethylammonium cation

Structural and vibrational features of Na-montmorillonite and montmorillonite intercalated with tetramethylammonium cation (TMA⁺) were characterized theoretically and experimentally. Theoretical study was performed using density functional theory with inclusion of dispersion corrections. The analysis of the hydrogen bonds in the calculated models has shown that the Na⁺ cations coordinated by six water molecules (Na-M model) are bound to montmorillonite layers by moderate hydrogen bonds between water molecules and basal oxygen atoms of the tetrahedral sheets. Hydrated Na⁺ cations are stabilized by relatively strong hydrogen bonds among water molecules. In the intercalate model, the TMA⁺ cation is fixed in the interlayer space by weak hydrogen bonds between the methyl groups and basal oxygen atoms of montmorillonite layers. The calculated vibrational spectra are in a good agreement with the measured infrared spectra. The detailed analysis of the simulated vibrational spectra allowed unambiguous identification of corresponding bands in the measured spectra and their assignment to the particular vibrational modes. For example, calculations clearly distinguished between AlMgOH and AlAlOH stretching vibrations and also between the coupled vibrations of the methyl groups of the TMA⁺ cations.     

Chiral derivatives of Butenafine and Terbinafine: synthesis and antifungal activity

Two series of allylamines/benzylamines have been synthesised and evaluated for their antifungal activity towards Cryptococcus neoformans. All compounds are chiral derivatives of Butenafine and Terbinafine, having additional substituents at the carbon connected to the central nitrogen atom. In both series, the antifungal activity was strongly dependent on both the steric bulk and the electronic nature of the substituents. Compared to the parent compounds (Butenafine and Terbinafine), the activity was maintained when the hydrogen was replaced with a methyl group. Lower activity was observed for ethyl, whereas introduction of -CH₂F, -CHF₂, -CF₃ or -CN substituents removed all antifungal activity. Testing of (R)- and (S)-N-(4-tert-butylbenzyl)-N-methyl-1-(naphthalen-1-yl)ethanamine against C. neoformans, Cryptococcus diffluens and Trichosporon cutaneum revealed that most of the activity resides in the (R)-enantiomer. The (R)-enantiomer performed as well as, or better (lower MIC values) than Butenafine against each test strain, suggesting that antimycotics based on this compound might be an improvement of existing Butenafine-based formulations.     

Thermal behaviour of intercalated 8-hydroxyquinoline (oxine) in montmorillonite clay

The composite montmorillonite-8-hydroxyquinoline (Swy-1-8-HQ) was prepared by two different processes and studied by using thermogravimetric analysis (TG/DTG and DSC), as well as helpful techniques as fluorescence in the UV-visible region and X-ray diffraction. The composites developed fluorescent appearance, however with quantum poor efficiency and they exhibited distinct TG and DSC thermal behavior. The fluorescence data of spectra associated to the TG/DT curves allowed to suggest that the 8-HQ was present in the composites in two different circumstances: 1 - intercalated in the interlayer spaces (Swy-1-8-HQ2), rigidly associated to the substrate feasible as a monolayer with the aromatic rings parallel to the silica layer; and/or, 2 - adsorbed on the surface (Swy-1-8-HQ1), either as a bilayer formation or tilting of the molecules to the silicate layer sheet. All results confirmed above are in agreement with X-ray diffraction patterns, once the interlayer space increases when 8-HQ is incorporated. The experimental results confirm the formation of the composites in agreement with the method used in the preparation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Zinc chelation and photofluorochromic behavior of spironaphthoxazine intercalated into hydrophobically modified montmorillonite

Spironaphthoxazine (SNO) and Zn2+ were intercalated into montmorillonite interlayers hydrophobically modified by the alkyltrimethylammonium cation during UV light irradiation. The fluorescence spectra of the montmorillonite composites were observed to vary with an increase in the UV and visible light irradiation times. These composites exhibited two types of fluorescence emissions: F1, which originates from a new species, Xs, which is different from SNO (ring-closed form) and merocyanine (MC; ring-open form), and F2, which originates from the MC-Zn complex. With increasing UV light irradiation time, the F1 intensities decreased, whereas the F2 intensities increased. Xs, which is an intermediate species between SNO and MC, was transformed into MC and then coordinated with Zn2+ (i.e., MC-Zn complex) during the UV light irradiation. The reaction rate of the formation of the MC-Zn complex decreased for the hydrophobically modified montmorillonite due to a longer alkyl chain. The retrieval changes in the F1 and F2 intensities were observed with an increasing visible light irradiation time, implying the dissociation of the MC-Zn complex into Xs and Zn2+. The dissociation especially occurred for the hydrophobically modified montmorillonite with a longer alkyl chain. The formation and disappearance of Xs and the MC-Zn complex obeyed first-order kinetics, and therefore the interconversion between Xs and MC could be regarded as the rate-determining step of the whole reaction during the UV and visible light irradiations. The photoinduced reactions of the SNO species and Zn2+ were profoundly affected by the physicochemical environment provided by the clay interlayers. It is concluded that the present photoreactions can be controlled not only by the amounts of the intercalated SNO species and Zn2+, but also by the hydrophobic environment created by the surfactant molecules.     

Models of (ZrO2)n complexes intercalated into montmorillonite

The article discusses the properties of several model zirconium dioxide complexes (ZrO(2))(n)() intercalated into the interlayer space of montmorillonite clay. Grand canonical Monte Carlo simulation was used in a series of numerical experiments during analysis of the low-temperature nitrogen adsorption in the micropores thus generated. The goal of such experiments was to determine the geometrical parameters of introduced molecular complexes of different types inside micropores of various widths. The obtained information was used to characterize textural and structural properties of three pillared interlayer materials prepared by using pillaring species synthesized via aging of zirconyl chloride solutions containing as additives chlorides of Ca, Sr, or Ba. It was found that in the cases of Ba and Ca the interlayer micropores are filled with isolated tetramers (ZrO(2))(4). Meanwhile, the presence of Sr in the pillaring solution, most likely, favors the preservation of larger sheetlike complexes (ZrO(2))(8).     

Montmorillonite-based porous clay heterostructures (PCHs) intercalated with silica-titania pillars—synthesis and characterization

Porous clay heterostructures (PCHs) were synthesized using natural montmorillonite as a raw material. Apart from pure silica pillars also silica-titania pillars were intercalated into the interlayer space of the parent clay. The detailed studies of the calcination process of the as-prepared PCH samples as well as thermal stability of the pillared structure of these materials were performed. The pillared structure of PCHs intercalated with both silica and silica-titania clusters was found to be thermally stable up to temperatures exceeding 600 °C. It was found that titanium incorporated into the silica pillars was present mainly in the form of separated tetracoordinated cations. For the samples with the higher Ti loading also small contribution of titanium in the form of the polymeric oxide species was detected. Titanium incorporated into the PCH materials significantly increased their surface acidity forming mainly Brønsted acid sites.     

Synthesis, characterization of mono, di and tri alkyl surfactant intercalated Wyoming montmorillonite for the removal of phenol from aqueous systems

Organoclays were synthesized by the ion exchange of cationic surfactants containing single, double and triple alkyl chains for sodium ions in an aqueous suspension of Wyoming Na-montmorillonite. The characterization of organoclays with and without adsorbed phenol was determined by X-ray diffraction, TEM and thermal analysis. Differences in the surfaces and in the interlayer of the mono, di and tri alkyl chain organoclays resulted in differences in the adsorption efficiency for phenol with tri > di > mono > Na-Mt. The results prove that organoclays can be effective for the removal of phenol from an aqueous solution and this removal is a function of the surfactant molecule and its concentration. In general, the higher the concentration as measured by the CEC value and the greater the number of alkyl chains in the surfactant molecule, the greater the percentage of the phenol that is removed.     

Non-isothermal crystallization kinetics of exfoliated and intercalated polyethylene/montmorillonite nanocomposites prepared by in situ polymerization

Polyethylene/montmorillonite (PE/MMT) nanocomposites, one intercalated sample with higher MMT content and one exfoliated sample with lower MMT content, were prepared by in situ polymerization using MMT-supported metallocene as catalyst. Non-isothermal crystallization behaviors of these two nanocomposites were investigated and compared. The exfoliated sample exhibits higher crystallization temperature (T_c) than the neat PE, showing nucleation effect of MMT. The intercalated sample has lower T_c than the neat PE due to the confinement of MMT. It is observed that the intercalated sample has longer induction period and faster overall crystallization rate, indicating co-existence of suppression and nucleation effects in this sample. The Avrami plots show that the crystal growth of PE in the intercalated sample is two-dimensional, while it is three-dimensional in the exfoliated sample. The crystallization activation energy of the intercalated sample is slightly smaller than that of the exfoliated sample.     

Montmorillonite intercalated with polyaminoamide-epichlorohydrin: preparation, characterization, and sorption behavior

Organophilic and cationic montmorillonite is desirable for pitch control in the pulp and paper industry. In this paper, polyaminoamide-epichlorohydrin (PAE)-modified montmorillonite was prepared via either solution intercalation or melt intercalation of polyaminoamide into montmorillonite, followed by the reaction with epichlorohydrin. The modified montmorillonite samples were characterized by FTIR spectroscopy, X-ray diffraction, and thermal gravimetric analysis. The amount of PAE intercalated and the surface charge densities of cationic-modified montmorillonite were determined. It was found that melt intercalation appeared to be more effective in the inclusion of PAE than solution intercalation. However, both solution- and melt-intercalated samples with various surface charge densities exhibited strong affinity toward dispersed colloidal rosin acid.     

Preparation and structure of highly confined intercalated polystyrene/montmorillonite nanocomposite via a two-step method

A two-step approach with a combination of emulsion polymerization and melt intercalation with higher clay loading of 33 wt.% is disclosed to highly confine the polystyrene (PS) chains by montmorillonite. The product of the emulsion polymerization is an easily crushable fine powder. And the powder is readily processible by open mill to form a transparent sheet. In the melt intercalation process, further intercalation of polystyrene narrows the space among the tactoids and results a highly confined intercalated nanocomposite. The results of dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC) showed that the cooperative motions of PS segments were substantially depressed, indicative of the highly intercalated structure formed in the nanocomposites. A structural model is proposed to explain the highly confined mesostruture of the PS/MMT nanocomposite.     

Preparation and characterization of anion‐exchange membranes derived from poly(vinylbenzyl chloride‐co‐styrene) and intercalated montmorillonite

In this paper, three organic intercalating agents containing cations [hexadecyl trimethyl ammonium bromide (CTAB), poly(acrylamide‐co‐diallyldimethylammonium chloride), and quaternized polyethyleneimine] are used to prepare intercalated montmorillonites (MMT) by ion‐exchange method. Then the modified MMTs are doped with vinylbenzyl chloride and styrene copolymer [poly(vinylbenzyl chloride‐co‐styrene)] for fabricating composite anion‐exchange membranes (AEM). Fourier transform infrared, X‐raydiffraction, thermogravimetric analysis, scanning electron microscopy, and Mastersizer laser particle size analyzer are employed to characterize the structure and morphology of MMTs and AEMs. The successful intercalation of MMTs is approved, and the MMT intercalated by CTAB shows an interlayer distance of 2.31 nm. The properties of the composite membranes including water uptake, mechanical property, and ionic conductivity are investigated. Among all the AEMs, the composite membrane containing MMT sheets with CTAB demonstrates better compositive performances. It presents an ionic conductivity of 2.09 × 10^?2 S cm^?1 at 80°C and good alkaline solution stability. Copyright © 2016 John Wiley & Sons, Ltd.     

TG characterization of organically modified montmorillonite

Montmorillonite was modified with octadecyltrimethylammonium chloride, under different reaction conditions, as evidenced by TG and XRD. TG curves presented two degradation peaks (295 and 395°C). At low salt concentrations, only the 395°C-degradation appeared, which increased with reaction time to the limit of 9 g of salt/100 g of clay. The second peak presented a limit at 17/100 m/m of salt/clay ratio. XRD analysis confirmed clay organic modification as the basal distance increased, showing greater reaction time effect than the salt mass effect, and with only one d-spacing. This suggested that an intercalation complex was formed but also that octadecyltrimethylammonium was adsorbed on the external surfaces of clay particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermogravimetric analysis of different molar mass ammonium cations intercalated different cationic forms of montmorillonite

Different cationic forms of montmorillonite, mainly K-, Na-, Ca- and Mg-montmorillonites were intercalated in this study via ion exchange process with mono-, di-, and triethanolammonium cations. The developed samples were characterized by TG, XRD, and CHNS techniques. Thermogravimetric study of ammonium-montmorillonites shows three thermal transition steps, which are attributable to the volatilization of the physically adsorbed water and dehydration, followed by the decomposition of the intercalated ammonium cations and dehydroxylation of the structural water of the modified clay, respectively, while untreated and cationic forms of montmorillonite showed only two decomposition steps. The type of ammonium cation has affected both desorption temperature (Position) and the amount of the adsorbed water (intensity). XRD results show a stepwise change in the crystallographic spacings of montmorillonite with the molar mass of ammonium cation, reflecting a change in the structure of the clay. CHNS data confirm the intercalation of ammonium cations into the interlayer space of montmorillonite and corroborate the effect of the molar mass of ammonium cation on the amount adsorbed by the clay.     

Preparation and characterization of intercalated misfit-layer compounds and natural superlattices

This paper presents the preparation and characterization of the new types of misfit-layer compounds and natural superlattices consisting of Ce_xNb_1−x−y□_yS (Q′) and Ni_zNbS₂ (H) layers, where □ is an atomic deficit at a metal site. A Q′ layer is larger by about 1 Å in thickness than a CeS (Q) layer in (CeS)_1.16NbS₂. They are prepared by chemical vapor transport reaction in a closed silica tube under quasi-equilibrium conditions. The 1Q′/3H type of compound are grown as a single crystal while the 1Q′/4H type of compound is grown as composite crystals with the 1Q′/3H and 1Q/2H compounds. Natural superlattices which have a long period in a direction perpendicular to layers are found. Their chemical formulae are given by (Ce_xNb_1−x−y□_yS)_m(Ni_z)_n−m(NbS₂)_n, where m and n are integers. It is found from an X-ray-photoelectron spectroscopy (XPS) study that Nb affects the valence and the bonding of Ce in the Q′ layers. It is in a higher oxidation state than Nb in NbS₂ layers. A scanning tunneling microscope (STM) study shows that some of the superlattices form a hexagonal supercell in the (a,b)-plane and behave as a narrow-gap semiconductor so that no STM images are obtained at bias voltage less than 0.3 eV.