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.

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.

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.

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.

Effect of montmorillonite on hydrate-based methane separation from mine gas

Three types of mine gas samples were used in the solutions of tetrahydrofuran(THF),sodium dodecyl sulfate(SDS)and THF-SDS with/without MMT respectively to investigate the effect of montmorillonite(MMT)on separation characteristics of methane recovered from mine gas based on hydrate method.The partition coefficient,separation factor and recovery rate were used to evaluate the effects of MMT,and the selection factor was primarily proposed to define the selectivity of mine gas hydrate in the relative target gases.The experimental results indicate that MMT could improve the following factors including hydration separation factor,the selection factor,the partition coefficient,and the recovery rate.Furthermore,the effect of SDS on the function of MMT is analyzed in the process of hydration separation.Finally,due to the results of the experiment,it is concluded that MMT hydration mechanism explores the effect of MMT enrichment methane from mine gas.

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.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.

Photocatalytic remediation ofγ-hexachlorocyclohexane contaminated soils using TiO_2 and montmorillonite composite photocatalyst

TiO2 and montmorillonite composite photocatalysts were prepared and applied in degrading γ-hexachlorocyclohexane （γ-HCH） in soils. After being spiked with γ-HCH, soil samples loaded with the composite photocatalysts were exposed to UV-light irradiation. The results indicated that the photocatalytic activities of the composite photocatalysts varied with the content of TiO2 in the order of 10%〈70%〈50% 〈30%, Moreover, the photocatalytic activity of the composite photocatalysts with TiO2 content 30% was higher than that of the pure P25 with the same mass of TiO2. The strong adsorption capacity of the composite photocatalysts and quantum size effect may contribute to its increased photocatalytic activities. In addition, effect of dosage of composite photocatalysts and soil pH on γ-HCH photodegradation was investigated. Pentachlorocyclohexene, trichlorocyclohexene, and dichlorobenzene were detected as photodegradation intermediates, which were gradually degraded with the photodegradation evolution.

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

DISPERSION AND TENSILE BEHAVIOR OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES PRODUCED VIA MELT INTERCALATION

Most of the articles on polymer nanocomposites focus on the importance of chemistry used to modify the surface of the clay, usually montmorillonite (MMT), and characterization of the nano-scale structure obtained. The role and importance of processing were also discussed recently. However, few papers concerning the correlation between morphology of MMT and mechanical properties were published. In order to understand. the tensile behavior of PP/Montmorillonite (MMT) nanocomposites better, and to further improve the reinforcement efficiency, we first prepared the PP nanocomposites via direct melt intercalation using conventional twin-screw extrusion. The dispersion and tensile property of the composites were then investigated by SEM, XRD, TEM and a video-controlled tensile set-up. The macroscopic and microscopic dispersion of MMT in PP matrix was verified by XRD and TEM, combined with SEM. The tensile properties were obtained by video-controlled tensile set-up, which gives true stress-strain curve. It was found that a partly intercalated and partly exfoliated structure (also called incomplete exfoliation) existed in the system. Though the tensile strength of PP nanocomposites is not much improved in engineering stress-strain curves, more than 20% increase of true stress was found in a true stress-strain experiment at high true strain, which indicates that only oriented silicate layers can have a big effect on tensile properties: Not only orientation of silicate platelets but also the degree of exfoliation is a key factor to determine the reinforcement efficiency. The reinforcement efficiency of MMT has been discussed based on the 'continuum' Halpin-Tsai equations. A good agreement was found between experimental data and theoretical prediction by changing N value (number of platelets per stack) which corresponding to different state of the dispersion of MMT in PP matrix.

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.

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.

Preparation and Characterization of Polylactide/Montmorillonite Nanocomposites

The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.

Atomic and electronic structures of montmorillonite in soft rock

Montmorillonite is a kind of clay mineral which often causes large deformation in soft-rock tunnel engineering and thus brings about safety problems in practice.To deal with these engineering safety problems,the physical and chemical properties of montmorillonite should be studied from basic viewpoints.We study the atomic and electronic structures of montmorillonite by using density-functional theory within the local-density approximation （LDA）.The results of calculation show that Al-O bond lengths are longer than Si-O bond lengths.It is found that both the valence band maximum （VBM） and the conduction band minimum （CBM） of montmorillonite are at point Г,and the calculated direct band gap of montmorillonite is 5.35 eV. We show that the chemical bonding between cations and oxygen anions in montmorillonite is mainly ionic,accompanied as well by a minor covalent component.It is pointed out that the VBM and CBM of montmorillonite consist of oxygen 2p and cation s states,respectively.Our calculated results help to understand the chemical and physical properties of montmorillonite,and are expected to be a guide for solving the problem of large deformation of soft-rock tunnels.

Acidic Montmorillonite/Cordierite Monolithic Catalysts for Cleavage of Cumene Hydroperoxide

In this work,a series of acidic montmorillonite/cordierite monolithic catalysts were prepared by a coating method using silica sol as the binder.The morphology and structure of the acidic montmorillonite/cordierite samples were characterized by means of X-ray diffraction(XRD),N_2 adsorption/desorption isotherms,and scanning electron microscope(SEM).The cleavage of cumene hydroperoxide(CHP) in a conventional fixed-bed reactor was chosen as a model reaction to evaluate the catalytic activity of the monolithic catalysts.The influences of acidic montmorillonite loading,reaction temperature.CHP concentration,and weight hourly space velocity(WHSV) on the catalytic activity and selectivity of phenol were studied.The results indicated that the obtained acidic montmorillonite/cordierite monolithic catalysts were firm and compact,and the loading of acidic montmorillonite was found to reach 40%(by mass) after three coating operations.The surface area of acidic montmorillonite/cordierite catalysts increases greatly as acidic montmorillonite loading increases due to higher surface area of acidic montmorillonite.Under the optimal reaction conditions(acidic montmorillonite loading of 32.5%(by mass),temperature of 80 ℃,a mass ratio of CHP to acetone of 1:3,and WHSV of CHP of 90 h^(-1)),the conversion of CHP can reach 100%,and the selectivity of phenol is up to 99.8%.

Design of Wood/Montmorillonite (MMT) Intercalation Nanocomposite

Studying new wood composites through nano science and technology (NSC) will develop new compounding theory of wood, and accelerate the combination of new technology, wood science, material science and other disciplines. The compounding of wood and inorganic MMT on nanoscale molecular level has high potential to greatly improve the mechanical properties, fire retardance, abrasion resistance, decay resistance, dimensional stability and other properties of wood. Based on the great achievements of polymer/montmorillonite (MMT) nanocomposites, this paper reviewed nano intercalation compounding methods (i.e. in-situ intercalative polymerization and direct polymer intercalation), and discussed the structure, properties and modification of montmorillonite (MMT). According to the main chemical components and particular structure of wood, the authors discussed the liquefaction and plasticization of wood, compared the dissolvability and meltability between wood and polymer, and then systematically put forward the basic idea, technological processes and schematic diagram to prepare wood/MMT nanocomposites (WMNC). The key technology to prepare WMNC is either to introduce delaminated MMT nanolayers into wood with the help of some intermediate polymers, or to obtain liquefied wood or plasticized wood from the complicated natural composite. It is applicable and effective to realize wood/MMT nanoscale compounding with the help of proper intercalation agent and medium polymer through the proposed 搊ne-step?or 搕wo-step?impregnating processes.

Adsorption of Environmental Pollutants on Pillared Montmorillonite

Both inorganic and organic pillared montmorillonites were used to adsorb phenol. Batch kinetics and isotherm studies were carried out to evaluate the effect of equilibrium time and pH on adsorption of phe- nol by montmorillonites and re-adsorbing characteristics of pillared montmorillonites. The adsorption of phenol increased with increasing solution pH values. The elimination ratio of phenol from the solution by the absorption of organic modified pillared montmorillonite (OrPMt) reached equilibrium quickly after vibrating for 5 minutes. Meanwhile for organic montmorillonite (OrMt), pillared montmorillonite (PMt) and montmorillonite (Mt), the time to reach phenol-absorption equilibrium were 20, 30 and 90 minutes, respectively. The adsorbing capacity of the pillared montmorillonite modified with surfactant improved greatly. The phenol-adsorbing capacity of pillared molltmorillonites mainly depended on microporous structure and surface component of the modified clays. After calcination at 500 ℃, the pillar structure and the basal spacing (1.83 um) were still stable. So the pillared montmorillonite could be recycled, and it was a potential material for adsorbing environmental pollutants.

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.