Preparation and Microstructure of Al-pillared Interlayered Montmorillonite

Al-pillared interlayered montmorillonite (Al-PILM) was prepared using the artificial Na-montmorillonite from the Qingfengshan bentonite mine as a starting material mixed with Al-pillaring solutions.The microstructure of the materials was studied by an X-ray powder diffractometer and a Fourier transform infrared (FTIR) spectrometer.The results indicated that the basal spacing [d(001) value] of the materials was increased significantly to 1.9194 nm relative to Na-montmorillonite (1.2182 nm).After calcined for 2 h at 300℃,the basal spacing was stabilized at 1.8394 nm and the layered structure of the materials was not destroyed.Thermal analysis was conducted by a thermal gravimetry and differential thermal analysis (TG-DTA) instrument,it showed that Al-PILM lost physically adsorbed water below 230.6℃ and water formed by dehydroxylation of the pillars at around 497.1℃, with a peak of the phase transformation at 903.0℃.

Swelling of K＋, Na＋ and Ca2＋-montmorillonites and hydration of interlayer cations： a molecular dynamics simulation

This paper performs molecular dynamics simulations to investigate the role of the monovalent cations K, Na and the divalent cation Ca on the stability and swelling of montmorillonite. The recently developed CLAYFF force field is used to predict the basal spacing as a function of the water content in the interlayer. The simulations reproduced the swelling pattern of these montmorillonites, suggesting a mechanism of their hydration different （K＋ 〈 Na＋ 〈 Ca2＋） from that of K＋-, Na＋-, and Ca2＋-montmorillonites. In particular, these results indicate that the valence of the cations has the larger impact on the behaviour of clay water systems. It also finds that the differences in size and hydration energy of K＋, Na＋ and Ca2＋ ions have strong implications for the structure of interlayer. This leads to the differences in the layer spacings of the simulated K＋-, Na＋-, and Ca2＋-montmorillonites. Furthermore, these simulations show that the K cations interact strongly with the clay sheets for the dehydrated clay sheets, but for the hydrated clays the Ca cations interact clearly strongly with the clay sheets.

Structure and antibacterial activity of Ce3+ exchanged montmorillonites

Four kinds of Ce3+ exchanged montmorillonites (Ce/MMTs) were prepared by an ion-exchange reaction, and characterized with energy dispersive X-ray analysis (EDX), X-ray difference (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The surface properties and antibacterial activity of Ce/MMTs were also investigated. The chemical compositions of Ce/MMTs were determined, and the cerium of Ce/MMTs was confirmed to be present as trivalent cerium state. The d001 basal spacings of Ce/MMTs were enlarged with the enhancement of the cerium contents, and the particles were formed with irregular shape. On increasing the Ce contents of Ce/MMTs, the special surface areas were decreased, but the total pore volumes and the average pore sizes were increased. The antibacterial activity of Ce/MMTs is increased with increasing the cerium contents, and 1.5 g/L of Ce/MMT-3 containing 11.46wt.% of curium could remove all the Staphylococcus aureus and more than 99.9% of the Escherichia coli within 24.0 h of contact. Moreover, Ce/MMTs displayed bactericidal activity.

A molecular dynamics study of the swelling patterns of Na/Cs-montmorillonites and the hydration of interlayer cations

We report on a molecular dynamics study of the swelling patterns of an Na-rich/Cs-poor montomorillonite and a Csmontomorillonite.The recently developed CLAYFF force field is used to predict the basal spacing as a function of the water content in the interlayer.The simulations reproduce the swelling patterns of the Na and Cs-montomorillonite,suggesting a mechanism of its hydration different from that of the montomorillonite.In addition,we find that the differences in size and hydration energy of Na and Cs ions have strong implications for the structure and the internal energy of interlayer water.In particular,our results indicate that the hydrate difference in the presence of coexistent Na and Cs has a larger influence on the behavior of a clay-water system.For Na-rich/Cs-poor montomorillonite,the hydration energy values of Na ions and water molecules each have a dramatic increase compared with those in Na-montomorillonite on the interlayer spacing,and the hydration energy values of Cs ions and water molecules decrease somewhat compared with those in Cs-montomorillonite.

Preparation and Characterization of Antibacterial Zn^(2+)-Exchanged Montmorillonites

Zn-montmorillonites（Zn-MMTs） as antibacterial compounds were prepared by an ion-exchange reaction. The reaction time, initial pH value and molar ratios of CEC influencing zinc content in Zn-MMTs were investigated, and Zn-MMTs were characterized by means of EDX, XRD, XPS, and SEM. The results of bacterial growth tests were confirmed by determination of the minimum inhibition concentrations （MICs） and minimum bactericidal concentrations （MBCs）. The experimental results show that the zinc is confirmed as bivalent zinc state, the d001 basal spacing of Zn-MMTs is enlarged with the enhancement of the zinc content, and the particles of Zn-MMTs are formed with irregular shape. Moreover, the antibacterial activity of Zn-MMTs increases with increasing the zinc content, and Zn-MMT-3 containing 6.76 mass% of zinc exhibits optimum antibacterial activity against Escherichia coli and Staphylococcus aureus.

Thermal stability and long-acting antibacterial activity of phosphonium montmorillonites

Na-montruorillonite （Na-MMT） was exchanged with three quaternary atkylphosphonium salts： decyl tributylphosphonium bromide （DTBPBr）, dodecyl tributylphosphonium bromide （DDTBPBr） and hexadecyl tributylphosphonium bromide （HDTBPBr）, to investigate the effects of phosphonium salts species and relative molecular mass on the characteristics, morphology, thermal stability and long-acting antibacterial property of phosphonium montmorillonites. The resulting modified montmorillonites were characterized by the FTIR, XRD, TEM, and TG/DTG techniques. And minimum inhibitory concentration （MIC） was used to investigate antibacterial activity. The results show that the phosphonium salts are intercalated into Na-MMT, and the basal spacing of P-MMTs is enlarged with the increase of phosphonium salt content or the growth of alkyl chain length. DDTBP-MMT-3 with 19.83% （mass fraction of dodecyl tributylphosphonium salts, displays excellent thermal stability and long-acting antibacterial activity.

Effect of different montmorillonites on rheological properties of bitumen/clay nanocomposites

Different composites of organomodified montmorillonite(OMMT)/bitumen were prepared by melt blending with hexadecyl dimethyl benzyl ammonium modified montmorillonite(HBM) and double octadecyl dimethyl ammonium modified montmorillonite(DOM).The structures of two kinds of montmorillonite modified bitumen were characterized by X-ray diffraction(XRD).The effects of different montmorillonites on the dynamic rheological properties of the modified bitumens were investigated by dynamic shear rheometer(DSR).The XRD results show that DOM modified bitumen forms an intercalated structure,whereas the HBM modified bitumen forms an exfoliated structure.DSR results indicate that OMMT modified bitumens exhibit higher complex modulus,lower phase angle than pristine bitumen,which means that the resistance to rutting at high temperatures of pristine bitumen is improved due to the introduction of OMMT.Compared with DOM modified bitumen,HBM modified bitumen shows better rutting resistance,which is contributed to the formation of exfoliated structure in HBM modified bitumen.

Organomontmorillonites Modified with 2-Methacryloyloxy Ethyl Alkyl Dimethyl Ammonium Bromide

Organomontmorillonites （organo-MMT） were synthesized by means of montmorillonites （MMT） modified with a series of 2-methacryloyloxy ethyl alkyl dimethyl ammonium bromide （MAAB） having different alkyl chain lengths as cationic surfactants through a cationic exchanging reaction, and were characterized by FTIR, TG, elemental analysis, and XRD. The microenvironment of the organic interlayer such as the orientation and arrangement of the alkyl chains of MAAB, as well as the properties of nanocomposite hydrogels, were also investigated. The amount of organic components absorbed on interlayer and the basal spacing of organo-MMT both increase with the increasing of alkyl length of MAAB. When carbon number of alkyl chain is in the region of 8 to 14, the alkyl chains between layers would adopt a disordered gauche conformation; while the carbon number is 16, an ordered all-trans conformation with a vertical orientation would be found together with the disordered gauche conformation according to the results of XRD and FTIR. Due to the difference of microenvironment of organic interlayer, the Young＇s moduli of the nanocomposite hydrogels increased as the alkyl chains of MAAB became longer.

On the Electric Conductivity of Homoionic Montmorillonites at Low Water Content

Bibliographic reports on the electric conductivity of pure homoionic montmorillonite at low water content were analyzed in order to stress a general behavior of conductivity. At low water content, the conductivity is attributed to a mechanism of charge transport involving protons due to the influence of the electric field of the exchangeable cations on water molecules at the solvation shell. Conductivity was analyzed in relation with the polarizing power （ionic potential） of the exchangeable cations and with the influence of the connectivity within samples. The general conclusion stressed is that the connectivity due to the association between 2：1 unit layers （clay fabric） is the main factor on the experimental or ＂macroscopic＂ electric conductivity of pure homoionic montmorillonite at low water content. Considerations on the experimental conditions of different bibliographic reports were also made. The conclusion and the considerations made on experimental conditions are a good starting point for future researches on electric conductivity ofhomoionic montmorillonite at low water content.

Preparation and Performance of Organically Modified Montmorillonite Composite Separation Membrane

A new composite separation membrane was developed by using organically modified montmorillonite(OMMT)as an additive.The effects of OMMT on the modification and properties of PVDF composite membranes were investigated.It is found that different kinds and amounts of OMMT into the casting solution can obviously change the pure water flux,separation performance and hydrophilicity of composite membrane in varying degrees.When the TA/PDA-MMT was 0.5 wt%,the pure water flux of the membrane reached the maximum,which was 584.7 L/(m^(2)·h),about 6 times that of the original membrane.The OMMT/PVDF composite membrane had good hydrophilicity and stability in the treatment of oily wastewater.The development of novel OMMT/PVDF composite membrane will provide a new idea for solving the problem of oily wastewater treatment.

Layer-by-layer fabrication of montmorillonite coating immobilizing Cu_(2)O nanoparticles for continuously catalyzing glycerol to dihydroxyacetone

Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.

The Structure of Montmorillonites Modified with Zwitterionic Surfactants and Their Sorption Ability

In the past four decades, there is a growing use of surfactant modified clay complexes in wide range of applications. The mostly used surfactants to modify the swelling clay minerals are cationic surfactants, such as quaternary ammonium, which consists of two distinct moieties, a hydrophilic head, where the positive charge is concentrated, and a hydrophobic hydrocarbon chain tail. During the surface modification, this kind of surfactant molecules attach on the inner and outer surface of clay minerals, the hydrophilic surface of raw clay minerals may changed into hydrophobic surface. The changes of organophilicity and hydrophobicity of clay minerals enable them used in more wide fields, such as adsorbents for organic contaminant, geotechnical barriers, filling of nanocomposite, etc.

High-temperature resistant polymer nanocomposites with exfoliated organic-modified montmorillonite nanosheets strongly adsorbed on polymer chains

It has been demonstrated that almost all polymer-clay nanocomposites show higher temperature stability than that of pure polymer, which is attributed to the active exfoliated clay nanosheet firmly adsorbed onto the polymer chains, due to polerization and nucleation effect, the clay nanosheets could protect the polymer chains from destroying. To prove such mechanism, the water-soluble polymer nanocomposites(AAA/SLS-MMT) were synthesized by the in-situ polymerization of 2-acrylamide-2-methyl-propane sulfonic acid, acrylamide, 4-acryloylmorpholine, and organically modified montmorillonite. The techniques of nuclear magnetic resonance, atomic force microscopy and scanning electron microscopy etc., clearly characterized the successful synthesized of sample's structure, the exfoliated MMT nanosheet adsorbed polymer chain's scale, and well-dispersed morphology, espectively. The adsorption model, X-ray photoelectron spectroscopy presented the existence of strong adsorption, while molecular simulation calculations first concluded that the strong adsorption energy was-13032.06 kcal/mol. Thermo-gravimetric-analysis proved the temperature of maximum thermal degradation of powder sample(AAA/1.0 wt% SLS-MMT) was over 298℃. After ageing at 180℃ for 4 h, the apparent viscosity of 5 g/L AAA/1.0 wt% SLS-MMT aqueous solution was 326.7 mPa,s, while that of pure polymer(AAA) was only 8.3 mPa,s. This optimized sample has the smallest FLAPIvalue at all test temperatures from 180 to 220℃ in both fresh and salt water based drilling fluid. All the evidences of high temperature resistance indicate that the strong adsorption can enhance the thickness of hydrated shell and adsorption of clay particles in drilling fluid at high temperature. Such mechanism supplied the better way to design high-temperature resistant fluid loss additives for deep and ultra-deep oil and gas formation engineering.

Vertically aligned montmorillonite aerogel-encapsulated polyethylene glycol with directional heat transfer paths for efficient solar thermal energy harvesting and storage

The conversion and storage of photothermal energy using phase change materials(PCMs)represent an optimal approach for harnessing clean and sustainable solar energy.Herein,we encapsulated polyethylene glycol(PEG)in montmorillonite aerogels(3D-Mt)through vacuum impregnation to prepare 3D-Mt/PEG composite PCMs.When used as a support matrix,3D-Mt can effectively prevent PEG leakage and act as a flame-retardant barrier to reduce the flammability of PEG.Simultaneously,3D-Mt/PEG demonstrates outstanding shape retention,increased thermal energy storage density,and commendable thermal and chemical stability.The phase transition enthalpy of 3D-Mt/PEG can reach 167.53 J/g and remains stable even after 50 heating-cooling cycles.Furthermore,the vertical sheet-like structure of 3D-Mt establishes directional heat transport channels,facilitating efficient phonon transfer.This configuration results in highly anisotropic thermal conductivities that ensure swift thermal responses and efficient heat conduction.This study addresses the shortcomings of PCMs,including the issues of leakage and inadequate flame retardancy.It achieves the development and design of 3D-Mt/PEG with ultrahigh strength,superior flame retardancy,and directional heat transfer.Therefore,this work offers a design strategy for the preparation of high-performance composite PCMs.The 3D-Mt/PEG with vertically aligned and well-ordered array structure developed in this research shows great potential for thermal management and photothermal conversion applications.

甲烷在钠基蒙脱土吸附的第一性原理研究

随着经济的发展,能源需求日益增加,为了弥补国内少油缺气短板,页岩气的开发成为近期新能源的热点,探索页岩气储存规律是页岩气能源开发的关键所在.本文采用密度泛函理论的第一性原理方法,计算甲烷(CH_(4))在钠基蒙脱土表面和层间的吸附能,对比吸附前后的态密度和物理结构以及差分电荷密度.结果表明:钠基蒙脱土表面吸附中,甲烷最佳选择是桥位,吸附能为-0.08eV,被吸附后甲烷的键长和键角变化率均小于0.96%.层间吸附中,伴随着甲烷吸附量增加,纳基蒙脱土体积向c轴方向线性增加,a、b轴方向则变化不大.总态密度随着吸附量的增加,总能级数量也增加,甲烷分子的分波态密度峰向低能级移动.本文的研究成果,从原子角度分析了甲烷在蒙脱石表面以及层间的吸附能力,为解释页岩气在页岩储存规律提供理论依据.

Study on the Mechanism of Innovative Montmorillonite for Diarrhea Treatment

[Objective] This study aimed to investigate the mechanism of innovative montmorillonite for diarrhea treatment. [Method] Thirty healthy weanling piglets （Duroc x Landrace x Yorkshire） were randomly divided into five groups and fed with basal diet, basal diet ＋ 1 g/kg innovative montmorillonite, basal diet ＋ 3 g/kg innovative montmorillonite, basal diet ＋ 5 g/kg innovative montmorillonite and basal diet ＋ 3 g/kg Bacillus subtilis microecologic agent, respectively. After four weeks, blood samples were collected via precaval vein, to detect the content of TFF3, NO and SOD in serum by ELISA kits. [Result] Compared with blank control group, the content of TFF3, NO and SOD in high-dose innovative montmorillonite group was extremely significantly increased, extremely significantly reduced and significantly in- creased, respectively; the content of TFF3 and NO in middle-dose innovative mont- morillonite group was significantly increased and significantly reduced, respectively. [Conclusion] Innovative montmorillonite may exert beneficial therapeutic actions on diarrhea by increasing TFF3 and SOD levels and decreasing NO level.

Cadmium adsorption in montmorillonite as affected by glyphosate

Behaviors of soil heavy metals are often affected by coexisting herbicides due to their physical and chemical interaction. Effect of glyphosate, an herbicide containing -PO 2- 3 and -COOH groups, on cadmium adsorption in montmorillonite was studied in detail. The results showed that the cadmium adsorption quantity in montmorillonite increased with increasing soil solution pH and cadmium concentration as usual, but decreased with glyphosate, which is due to the formation of a low affinity complex of Cd and glyphosate and decreasing solution pH induced by glyphosate addition. When the equilibrium solution pH was below 6.7, glyphosate has little effect on cadmium adsorption, but when the equilibrium solution pH was above 6.7, glyphosate significantly decreased cadmium adsorption quantity in montmorillonite. In addition, the adding order of Cd and glyphosate also influenced Cd adsorption quantity in montmorillonite.

Extractive oxidative desulfurization of model oil/crude oil using KSF montmorillonite-supported 12-tungstophosphoric acid

12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide（H2O2） as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds（S-compounds） molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene（DBT） and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.

Preparation and Properties of Gelatin-Chitosan/Montmorillonite Drug-loaded Microspheres

A kind of slow release drug-loaded microspheres were prepared with gelatin, chitosan and montmorillonite（MMT） by an emulsification/chemical cross-linking method using glutaraldehyde as cross-linking agent and acyclovir as model drug. The microspheres were characterized by X-ray diffraction （XRD）, Fourier transform infrared （FT-IR） and scanning electron microscopy （SEM）, respectively. The morphology, drug content, encapsulation efficiency and drug-release behavior were investigated with different MMT contents. The experimental results indicated that intercalated microspheres could be prepared, the morphology of microspheres was markedly affected by MMT. The glomeration performance of uncross-linked microspheres was improved because of the physical cross-linking of MMT. Drug content and encapsulation efficiency were decreased when increased the content of MMT, but burst release and the drug release were significantly decreased with the addition of MMT. Effective physical cross-linking could be formed when added MMT, and MMT could reduce the content of toxic chemical cross-linking agents.

Synthesis of ethyl acetate by esterification of acetic acid with ethanol over a heteropolyacid on montmorillonite K10

In present work,liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid （DTPA） supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out.The 20% m/m DTPA/K10 was found to be the optimum catalyst with 90% acetic acid conversion and 100% ethyl acetate selectivity.The study was also explored to see the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of acetic acid with other alcohols like methanol,iso-propanol and n-butanol.The 20% m/m DTPA/K10 has shown increased activity with the increase in carbon number,at the same alcohol reflux.The results are novel.