Interlayer Space Of Montmorillonite Research Articles

Structure and Intercalation of Cysteine-Asparagine-Serine Peptide into Montmorillonite as an Anti-Inflammatory Agent Preparation-A DFT Study.

Peptides are receiving significant attention in pharmaceutical sciences due to their applications as anti-inflammatory drugs; however, many aspects of their interactions and mechanisms at the molecular level are not well-known. This work explores the molecular structure of two peptides-(i) cysteine (Cys)-asparagine (Asn)-serine (Ser) (CNS) as a molecule in the gas phase and solvated in water in zwitterion form, and (ii) the crystal structure of the dipeptide serine-asparagine (SN), a reliable peptide indication whose experimental cell parameters are well known. A search was performed by means of atomistic calculations based on density functional theory (DFT). These calculations matched the experimental crystal structure of SN, validating the CNS results and useful for assignments of our experimental spectroscopic IR bands. Our calculations also explore the intercalation of CNS into the interlayer space of montmorillonite (MNT). Our quantum mechanical calculations show that the conformations of these peptides change significantly during intercalation into the confined interlayer space of MNT. This intercalation is energetically favorable, indicating that this process can be a useful preparation for therapeutic anti-inflammatory applications and showing high stability and controlled release processes.

Enhancing fire performance and thermal stability of flexible PVC with lanthanum phytate montmorillonite

This study presents a breakthrough approach to enhance the thermal stability, mechanical properties, and flame retardancy of flexible PVC (fPVC). It introduces lanthanide phytate montmorillonite (Pa-La-Mt) as an innovative nanofiller. Pa-La-Mt was synthesized by intercalating sodium phytate and lanthanum chloride into the interlayer space of montmorillonite (Mt), effectively increasing the layer spacing. The analysis of this study, using X-ray diffraction (XRD) and Fourier infrared spectrometer (FTIR), confirmed this structural transformation. The influence of Pa-La-Mt on the structural and performance aspects of fPVC composites was thoroughly examined. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), mechanical testing, limit oxygen index (LOI), and cone calorimeter (CONE) revealed compelling outcomes. Pa-La-Mt not only improved the dispersion and compatibility of Mt. within the fPVC matrix but also enhanced the thermal stability and mechanical performance of fPVC composites. Most notably, Pa-La-Mt exhibited remarkable flame retardant and smoke suppression effects on fPVC composites. It led to a substantial increase in LOI value, a reduction in the peak heat release rate and total heat release amount, and a decrease in CO and CO2 emissions. This underlines Pa-La-Mt as a promising nanofiller with profound implications for various fPVC applications.

Adsorption of Ciprofloxacin on Clay Minerals in Argentinian Santa Rosa-Corrientes Soils.

The presence of antibiotics in soils is increasing drastically in last decades due to the intensive farming industry and excessive human consumption. Clay minerals are one of the soil components with great adsorption capacity for organic pollutants. The study of interactions between antibiotics and mineral surfaces will give us scientific knowledge of these pollutants through soils. In this work, we study the adsorption of the antibiotic ciprofloxacin in the clay mineral fraction of soils from the Argentinian zone of Santa Rosa (Corrientes), in a collaborative research of experiments and atomistic modelling calculations of the intercalation of ciprofloxacin in the interlayer space of montmorillonite. Adsorption and desorption isotherms were performed and compared with different isotherm models. Additionally, enthalpy, entropy, and free energy were determined from equilibrium constants at a function of temperature. All these experiments and calculations lead to the conclusions that two adsorption types of ciprofloxacin are found on clay minerals: one weakly sorbed that is released during the desorption experiments, and other one strongly joined that remains in the soil.

Insights on adsorption of pyocyanin in montmorillonite using molecular dynamics simulation.

Pyocyanin is an important virulence factor in the resistance of Pseudomonas aeruginosa to antibiotics. Pyocyanin is a planar three ring aromatic molecule that occurs as zwitterionic (PYO) or protonated species (PYOH+). Our earlier studies have shown that montmorillonite, through adsorption and transformation, can inactivate both PYO and PYOH+ in the interlayer space. The objective of this study was to elucidate the interaction mechanisms between montmorillonite and the adsorbed pyocyanin and to characterize the structure of the pyocyanin-montmorillonite complex via molecular dynamics (MD) simulations. The MD simulations were performed for the complexes of hydrated Na-montmorillonite (HM) with (i) neutral pyocyanin (HMP) and (ii) protonated pyocyanin (HMPH); and dehydrated Na-montmorillonite (DM) with (iii) neutral pyocyanin (DMP) and (iv) protonated pyocyanin (DMPH). The simulations indicated that in dry conditions, both PYO and PYOH+ were well-ordered in the midplane of the interlayer of montmorillonite, with the three aromatic rings almost parallel to the basal surface and sandwiched in-between basal surface-adsorbed Na+ planes. In humid conditions, the pyocyanin and Na+ were solvated in the interlayer space and the pyocyanin was less ordered compared to dehydrated models. Ion-dipole interaction (Na-O) was the dominant interaction for the dehydrated complexes DMPH and DMP but the interaction was stronger in the latter. The Na-O ion-dipole interaction remained the dominant interaction in hydrated HMP while in HMPH, water outcompeted PYOH+ for Na+ resulting in water-Na interaction being the dominant interaction. These results revealed the arrangement of the two species of pyocyanin in the interlayer spaces of montmorillonite and the mechanism of interaction between the pyocyanin and montmorillonite.

Structure and mobility of rare earth ions in interlayer space of montmorillonite: a molecular dynamics study.

Ion adsorption-type deposits (IADs) are the dominant sources of rare earth elements (REEs), in which REEs are mainly enriched in clay minerals. However, the adsorption mechanism of REEs in the interlayer region of clay minerals is still poorly understood. In this study, by using molecular dynamics (MD) simulations, we explored the interlayer structures and dynamics of REEs-intercalated montmorillonite. La3+ and Lu3+ were used as the model cations for light REEs (LREEs) and heavy REEs (HREEs), respectively. It was found that the most thermodynamically stable state for both LREE- and HREE-montmorillonite was the double-hydration state and the corresponding basal spacing was calculated to be ∼16.1 Å. REE ions are located at the middle plane of the interlayer space and adsorbed on the montmorillonite basal surface through hydrogen bonds between its coordination water and the basal oxygens (i.e. as outer-sphere complexes). La3+ was 9-fold coordinated in the interlayer space with a mono-capped square antiprism coordination shell, while Lu3+ was 8-fold coordinated in a square antiprism cage. The mobility of REEs intercalated in the interlayer was significantly reduced compared to the mobility of REEs in aqueous solutions. The microscopic structures, thermodynamic data, and mobility obtained in the present study can help understand the enrichment and mobilization of REEs in IADs, and provide a molecular level basis for developing more efficient extraction techniques.

Thermal Stability and Resistance to Biodegradation of Humic Acid Adsorbed on Clay Minerals

This article studies sorption regularities and evaluates thermal stability and resistance to microbial degradation of humic acid during three sorption cycles on bentonite clay, kaolinite, and muscovite using TGA/DSC, XRD, hydrophobic chromatography, light and electron microscopy, etc. The experiment revealed that kaolinite sorbed more humic acids (HAs) in terms of unit surface area (1.03 × 10−3 C, g/m2) compared to bentonite (0.35 × 10−3 C, g/m 10−3 g/m2). Sorption at pH 4.5 showed HA fractionation in amphiphilicity and chemical composition. HA was sorbed on the surface of all sorbents, mainly via hydrophobic components. No intercalation of HA into the interlayer spaces of montmorillonite was observed during sorption. Sorption via hydrophilic interactions was mostly performed on muscovite and bentonite rather than on kaolinite. Sorption of HA resulted in changes in its chemical composition and decreased C/N compared to free HA, which demonstrated selective sorption of nitrogen-containing compounds more typical of muscovite. All minerals adsorbed only a relatively thermolabile HA fraction, while its thermal stability increased compared to that before the experiment. The thermal stability and ratio of the Exo2/Exo1 peak areas on the DSC curves of sorbed HA increased with each subsequent sorption cycle. We revealed the following relationship between thermal stability and resistance to microbial oxidation of the sorbed HA: The higher the thermal stability, the less available the sorbed HA becomes for utilization by microorganisms.

Prospects for Application of Guanidine-Containing Organomineral Complexes as Biocidal Functional Additives for Waterborne Polymer Materials

The possibility of using organomineral complexes of polyhexamethylene guanidine hydrochloride as a functional additive for a waterborne paint based on polyvinyl acetate has been investigated. Organomineral complexes containing 20 and 30 wt % guanidine polymer have been obtained, with intercalation of polyguanidine chains into the interlayer space of montmorillonite being observed. It has been revealed that the stability of the polymer film to water is retained when organomineral complexes are introduced into a polyvinyl acetate dispersion, whereas the water resistance of the film sharply decreases when free polyguanidine is added. There was no significant influence of organomineral complexes on the rheological characteristics of the dispersion and its sedimentation stability. Testing of waterborne paints with various additives has shown that introduction of organomineral complexes into the material prevents the coating from fouling by biofilms of gram-positive bacteria Staphylococcus aureus and Rhodococcus erythropolis, with the hardness, water resistance, and water-vapor transmission of the coatings being retained at a satisfactory level.

Intercalation of sulfonamides in montmorillonite by molecular dynamics and DFT calculations for bioavailability control

The intensive use of antibiotics and especially sulfonamides in the livestock industry is getting an alarming level. The presence of these drugs in wastewaters, rivers and underground waters is increasing considerably in developing countries. The molecular interactions of these drugs with the surfaces of clay minerals can be interesting for evaluating their mobility in soils and for preparing composite complexes for optimal use. In this work, the intercalation of antibiotics derivatives of sulfonamides, such as sulfamethazine, sulfamethoxazole, sulfachloropyridazine and sulfacetamide, into the interlayer space of montmorillonite (MNT) is studied at molecular and 3-D periodical crystal structure level by using computational modeling, molecular dynamics and calculations based Density Functional Theory (DFT). Most of these intercalations are energetically favourable, where the role of water molecules is critical. In general, the bioavailability of these compounds by intercalation in MNT is bigger than from the crystalline powder. Spectroscopic properties of these systems showed interesting frequency shifts in the bands of the IR spectrum produced during the intercalation in the confined space of MNT. These results predict that the IR spectroscopy as an interesting analytical technique for monitoring the intercalation of drugs in clay minerals.

An extended model based on the general Van Genuchten model for the “wetting” process of GMZ Na-bentonite subjected to alkali-heat treatment

During the long-term operation of a nuclear waste repository, the buffer/backfill material in the shield of the repository can eventually lose the ability to retain water owing to factors such as groundwater chemistry and heat released from nuclides. In this paper, a test platform was constructed to investigate the “wetting” behavior of GMZ Na-bentonite (a local bentonite from Gaomiaozi county, China) after being subjected to different alkali-heat treatments (AHTs). The experimental results show that (i) montmorillonite primarily decomposes and dissolves under the alkali-heat conditions, (ii) the mass moisture content and equivalent crystalline interlayer (ECI) space of montmorillonite are negatively correlated with the duration and temperature of AHT and (iii) independent of AHT, the evolutionary relationship between the mass moisture content and suction of montmorillonite exhibits a rapid decrease in the low-suction range and a gradual stabilization in the high-suction range. Significantly, an extended VG (EVG) model was developed to quantitatively characterize impact of temperature and alkaline solution on weakening the ability of bentonite to retain water. The developed model considers the contribution of the spatial perturbation factor to the saturation, so as to clearly characterize the three “wetting” states of bentonite in ascending order of the matric potential: water-linked & air-closed, water–air fully open, and water-closed & air-linked.

Tin sulfides and cadmium sulfide mixture in montmorillonite with enhanced visible-light photocatalytic activity

In situ formation of tin sulfide (SnS) and cadmium sulfide (CdS) mixture in montmorillonite was carried out by the reaction between an aqueous dispersion of Sn2+- and Cd2+-montmorillonite and an aqueous solution of S2− (from Na2S). The effects of Sn2+ / Cd2+ molar ratios were examined. The appearance of two diffraction peaks (d001 = 1.3 and 1.4 nm) and/or the large mismatch (8%) of SnS and CdS lattices were attributed to the possible formation of SnS and CdS in two different interlayer spaces (segregation) of montmorillonite. The blue shifts of the absorption onset relating to the expansion of band gap energy, and the emission band as well as the increase of emission intensity of the intercalated SnS and CdS mixture were observed with increasing SnS / CdS molar ratio. The photodegradation of rhodamine 6G solution was achieved within 360 min by using the product, which has the molar ratio of Sn / Cd = 3:1. The photocatalytic process followed pseudo-first-order kinetic with a rate constant of 0.011 min−1. The scavenger test indicated that superoxide radical (O2•-) was the predominant species involved in the photocatalytic process. This result represented an important role of montmorillonite and the heterostructures of SnS and CdS in tailoring the photocatalytic properties.

Montmorillonite as an Anti-Tuberculosis Rifampicin Drug Carrier: DFT and Experimental Study

A hybrid of montmorillonite (Mnt) and rifampicin (RIF) was synthesized and the structure and stability of the drug carrier system clarified. Density functional theory calculations involving dispersion corrections (DFT-D3) were performed to characterize interactions acting in the interlayer space of montmorillonite intercalated with rifampicin. The structure and stability of the RIF-Mnt intercalated complex were determined. Calculations revealed the deformation of the molecular structure of rifampicin after intercalation into the Mnt interlayer space due to the clay environment. The ansa chain of RIF was bent in the interlayer space compared with the structure of the RIF molecule in the monocrystal. RIF was keyed into the Mnt surface by means of numerous hydrogen bonds of weak to moderate strength. The calculated vibrational spectrum from ab initio molecular dynamics (AIMD) was in good agreement with the FTIR measured spectra and helped to analyze the overlapped vibrational bands. Based on analysis of structural stability, theoretical calculations revealed that Mnt is a suitable drug carrier for delayed release of the RIF drug. Batch adsorption experiments showed the large adsorption capacity of montmorillonite for RIF.

The important role of surface hydroxyl groups in aluminum activation during phyllosilicate mineral acidification

Phyllosilicate minerals are the important components in soils and an important source of activated aluminum (Al) during soil acidification. However, the mechanisms for Al activation in phyllosilicate minerals were not understood well. In this paper, the effect of phyllosilicate surface hydroxyl groups on Al activation during acidification was studied after the minerals were modified with inorganic and organic materials. After modification of kaolinite, montmorillonite, and illite with fulvic acid (FA-), iron oxide (Fe-), Fe combined with FA (Fe-FA-), and siloxane (Si–O-), the interlayer spaces were altered. For instance, when modified with Fe, Fe entered the interlayer spaces of kaolinite and montmorillonite and changed the interlayer spaces of both minerals but did not affect that of illite. Also, the other modification methods had significant effects on the interlayer space of montmorillonite but not on kaolinite and illite. It was observed that all the modification strategies inhibited Al activation during acidification by reducing the number of hydroxyl groups on the mineral surfaces and inhibiting protonation reactions between H+ and hydroxyl groups. Nevertheless, the inhibition effect varies with the type of phyllosilicate mineral. For kaolinite (Kao), the inhibition effect of the different modification methods on Al activation during acidification followed: Fe-FA-Kao > Fe-Kao > Si–O-Kao > FA-Kao. Additionally, for montmorillonite (Mon), the inhibition effect was in the order: Si–O-Mon > Fe-Mon > Fe-FA-Mon > FA-Mon, while for illite, it was: Fe-illite > Si–O-illite ≈ Fe-FA-illite > FA-illite. Thus, the hydroxyl groups on the surfaces and edges of phyllosilicate minerals play an important role in the activation of Al from the mineral structure. Also, the protonation of hydroxyl groups may be the first step during Al activation in these minerals. The results of this study can serve as a reference for the development of new technologies to inhibit soil acidification and Al activation.

THE EFFECT OF DISPERSION TIME ON THE STRUCTURE AND THERMOPHYSICAL PROPERTIES OF SYSTEMS BASED ON POLYETHYLENE GLYCOL AND MONTMORILLONITE

In this work, the effect of ultrasonic dispersion time on the structural and thermophysical properties of nanocomposites was studied. Model systems were made based on polyethylene glycol and montmorillonite. All samples had the same composition and filler content (5% by weight), the ultrasonic treatment time was from 5 to 12 minutes. The methods of wide-angle X-ray scattering and differential scanning calorimetry were used to establish the dependence of the properties of the systems on the dispersion time. Data analysis of the obtained results showed that the variation of ultrasonic dispersion time significantly affects the properties of polymer nanocomposites. As the mixing time increases, the interplanar distance of montmorillonite increases, which indicates an increase in the degree of intercalation of the polymer matrix. At the same time, the crystallinity of the nanocomposite decreases, which corresponds to the increase in the area of the polymer/filler boundary layer. The melting temperature of the nanocomposite increases with increasing dispersion time. This trend is a consequence of the complication of the thermal movement of polymer molecules due to the presence of a developed surface of the filler. It is shown that with an increase in the sonication time, the part of the immobilized amorphous fraction of the polymer increases. This is explained by the fact that the polymer intercalated in the interlayer space of montmorillonite loses its ability to cooperative movement, that is, to glass transition. It was established that the maximum improvement of system properties is observed at a dispersion time of 10 min. In this state, the montmorillonite particles are most stratified, which leads to the maximum increase in the area of the boundary layer. During further mixing, processes of aggregation of montmorillonite particles and destruction of polymer molecules occur, which leads to the loss of the desired properties of the nanocomposite. Finding the optimal mixing time of a polymer nanocomposite makes it possible to obtain the desired properties of systems with a defined composition.

Adsorption of Capsaicin into the Nanoconfined Interlayer Space of Montmorillonite by DFT Calculations

Capsaicin is the main compound responsible of the hot sense of the chili fruits. This compound has interesting therapeutic properties including anticancer, anti-inflammatory effects, and analgesic. However, its use has several secondary effects, such as skin irritation and allergies. Then, new therapeutic strategies are searched in order to overcome these problems. Montmorillonite has proved to be an excellent excipient for the release of pharmaceutical drugs. In this work, the molecular structure and crystal structure of capsaicin, and the adsorption of this molecule into the interlayer space of montmorillonite have been studied using quantum mechanical calculations based on Density Functional Theory (DFT) level of theory and molecular dynamics simulations. The crystal structure has been predicted with these calculations and the intermolecular interactions have been determined with a higher resolution than the previous experimental data. The adsorption of capsaicin into the confined interlayer space of montmorillonite is energetically favourable with low and high octahedral charge. This adsorption can be monitored by IR spectroscopy observing frequency shifts in some bands during the adsorption. This enhances the use of these clay minerals for capsaicin therapeutic formulations.

Preparation and structure analyses of Sn-bentonite for pertechnetate removal

Tin (Sn) -bentonite was prepared by ion exchange method from Ca-bentonite. For the ion exchange process, tin-chloride (SnCl2) solution was prepared from metallic tin, and the tin concentration was determined by Microwave Plasma Atomic Emission Spectroscopy (MP-AES). Sn-bentonite was characterized by X-ray fluorescence spectrometry (XRF), X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS) and 119Sn as well as iron-57 (57Fe) Mössbauer spectroscopy. 119Sn Mössbauer spectroscopy and XPS undoubtedly revealed both Sn+2 and Sn+4 ions in Sn-bentonite. SnII was attributed to be incorporated into the interlayer space while SnIV located partly in the octahedral position and in the interlayer space of montmorillonite. The removal of radioactive pertechnetate anion (99mTcO4-) was studied on Sn-bentonite in aqueous and artificial urine media. Based on the measurement results, 99mTcO4- ion can be removed, in case of aqueous media, the equilibrium is reached after 5 mins (x = 99.9 ± 0.01%, k = 4.2 ± 0.83 1/min) (Buzetzky et al., 2019), while in the case of urine media the equilibrium is reached after 30 mins (x = 59.1% ± 2.7, k = 0.18 ± 0.05 1/min). Pertechnetate anoin sorption on tin-bentonite is a (Sn(II/IV)-TcO4-) redox reaction. Thus, Sn-bentonite can be a suitable sorbent for radioactive waste management.

Development and characteristics of layered EGCG/Montmorillonite hybrid: An oral controlled-release formulation of EGCG

An oral controlled-release formulation of epigallocatechin-3-gallate (EGCG) was developed by intercalating EGCG into the interlayer space of Food and Drug Administration-approved mucoadhesive montmorillonite (Mt) nanolayers, and characterized by ultraviolet–visible, X-ray diffraction, Fourier transform infrared, and thermogravimetry. The EGCG intercalation was only possible at acidic pH, and occurred through electrostatic and hydrogen bonding interactions allowing restacking of exfoliated Mt nanolayers with EGCG molecules. It was inferred that EGCG molecules were adsorbed flat on the interlayer surface of Mt in a monolayer and formed two-sided hydrogen bonds with the Mt faces, leading to a ∼2-fold increase in the EGCG decomposition temperature. A maximum EGCG loading of ∼40 wt% was achieved at pH 3, reaction time 1 h, and EGCG:Mt ratio 40:10 mg/mL. The EGCG/Mt hybrid showed a sustained release of EGCG in simulated gastric and intestinal fluids in a pH-dependent manner. Deprotonation of EGCG was responsible for further EGCG release at pH 7.4 compared to pH 1.2. The release profiles were fitted to the parabolic diffusion and Bhaskar models, implying that the release was controlled by a diffusion process. These results suggest that Mt with a high loading capacity can be used as the controlled-release nanocarrier of EGCG in oral administration.

Development of novel montmorillonite-based sustained release system for oral bromopride delivery.

The drug delivery systems are an important strategy of pharmaceutical technology to modulate undesirable properties, increasing efficacy, and reducing the side effects of active pharmaceutical ingredients (API). The sustained release is a type of controlled-release system that provides a suitable drug level in the blood through a slow release rate. An interesting alternative to achieve a controlled release is the application of carrier materials such as polymers, cyclodextrins, and clays. Sodium montmorillonite (Na-MMT) is a biocompatible natural clay that allows the insertion of organic compounds in interlamellar space, owing to its high cation exchange capacity and large internal surface area. Bromopride (BPD) is an aminated compound with antiemetic properties classified as class II (low solubility, high permeability) of the Biopharmaceutical Classification System (BCS). Herein, the aim of the study was the development and investigation of a drug delivery system formed by intercalation of BPD with Na-MMT. The results indicate the successful intercalation of this API with the lamellar silicate, meanwhile, there was no evidence of BPD intercalation in organic montmorillonite. The Na-MMT/BPD molecular complex exhibits a sustained release in performed assays. Molecular dynamics simulations suggested that BPD molecules interact with the montmorillonite layer through ion-dipole interactions and also between BPD molecules, forming hydrogen bonds web into montmorillonite interlayer space. The new drug delivery system showed an alternative to achieve the BPD sustained release, which may improve its pharmacological performance in therapeutic applications.

The influence of technological conditions and molecular weight of PEG on basal spacing of Vietnamese bentonite

AbstractThe unique expansion properties of the interlayer space of montmorillonites allow for surface modification of bentonite. PEG is a nonionic polymer that can adsorb and intercalate into the interlayers of bentonite. The results of FTIR and TGA spectra allow confirming that PEG has not only covered bentonite but also inserted into the interlayers of bentonite. Therefore, the modified product can be applied not only as a dispersant in polymer composites, but also as an adsorbent. Moreover, a variety of technological factors affecting modification have been studied and the most suitable conditions have been proposed. In which, temperature, stirring speed, time and suspension concentration were selected at 25°C, 800 rpm, 8 h and 2 wt.%, respectively. The influence of the component ratio (Ben/PEG) on the modification process was also studied. The most suitable Ben/PEG ratio for each PEG type was also given. The results show that the interlayer spacing in modified bentonite depends not only on the technological conditions, the composition ratio but also on the molecular weight of PEG. Thus, the choice of PEG for bentonite modification will determine the d001 basal spacing of modified product.

Dispersion and Swellability of Ternary Surfactant Co-Modified Montmorillonites

AbstractOrgano-montmorillonite (OMnt) has wide applications in paints, clay-polymer nanocomposites, biomaterials, etc. In most cases, the dispersibility and swellability of OMnt dictate the performance of OMnt in the target products. Previous studies have revealed that the properties can be improved when multiple organic species are co-introduced into the interlayer space of montmorillonite (Mnt). In the present study, single surfactant erucylamide (EA), dual-surfactants cetyltrimethyl ammonium bromide (CTAB) and octadecyltrimethyl ammonium chloride (OTAC), and ternary-surfactants EA, CTAB, and OTAC were co-introduced into Mnt by solution intercalation. The resulting OMnts were characterized by powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetry-differential thermogravimetry (TG-DTG), water contact-angle tests, scanning electronic microscopy (SEM), laser particle-size analysis, and swelling indices. Mnt co-modified by ternary CTAB, OTAC, and EA led to a large d001 value (4.20 nm), surface hydrophobicity with a contact angle of 95.6°, swellability (50 mL/g) with small average particle sizes (2.1−2.8 μm) in xylene, and >99% of the OMnt particles were kept as <5 μm in deionized water. The formation of EA-modified-Mnt was proposed according to hydrophobic affinity, hydrogen bonding, and van der Waals forces. The nanoplatelets of the CTA+, OTA+, and EA co-modified OMnts in xylene were assembled into a house-of-cards structure by face-to-edge and edge-to-edge associations. The electrostatic attractions, electrostatic and steric repulsions, and hydrophobic interactions were responsible for the good dispersibility of OMnt in xylene. The ternary surfactant co-modified OMnt with high dispersion and swellability will make OMnt better suited for real-world applications.

Recent advances in engineering montmorillonite into catalysts and related catalysis

ABSTRACT Montmorillonite, a ubiquitous clay mineral, has been engineered into a variety of porous and nanostructured catalysts, owing to its peculiar layered structure with characteristic surface and intercalation chemistry. Such a class of catalysts have continuously received considerable attention in both science and industry. This review examines recent advance in engineering montmorillonite into metal ion-exchanged montmorillonite catalysts, acid-activated montmorillonite catalysts, organo-montmorillonite catalysts, pillared interlayered montmorillonite catalysts and montmorillonite-supported catalysts. The former two types of montmorillonite-based catalysts have been used in the catalytic cracking, dehydration, hydrolysis, esterification, polymerization, alkylation, and Fischer-Tropic synthesis. The introduction of oxide pillars in the interlayer space of montmorillonite and the immobilization of metal oxides or zero-valent metals on the surface of montmorillonite allow montmorillonite to be used in the catalytic oxidation, reduction, isomerization and coupling reactions. Currently, the role of montmorillonite in acid catalysis, redox catalysis, and free radical catalysis have been partly revealed. The effect of the structures and the active sites of modified montmorillonite on its catalytic performance need to be investigated in more detail. Future work is suggested to focus on solving engineering problems and exploring novel catalytic applications of montmorillonite, in particular exfoliated montmorillonite nanolayers.