含过渡金属离子的交联蒙托土交联柱中Keggin结构的作用

利用Keggin结构可以发生同晶取代的性质,合成了含过渡金属离子铬、镍的羟基铝交联蒙托土,并运用XRD、~(27)Al-NMR、UV-DRS、XPS、TPR等方法研究了Keggin结构的作用。结果表明,铬、镍都可以和铝生成具有Keggin骨架结构的羟基共聚体,并以此作柱子支撑着蒙托土的层间。铬的取代反应比镍容易发生。共聚法合成出的羟基镍铝交联蒙托土中镍存在两种状态;过量的金属离子对Keggin结构有较大地破坏;Keggin结构的存在增加了交联蒙托土的热稳定性。     

Effect of the acid activation levels of montmorillonite clay on the cetyltrimethylammonium cations adsorption

For the first time, the intercalation properties of acid-activated montmorillonites treated at different acid/clay (w/w) ratios with a cationic surfactant cetyltrimethylammonium (C16TMA) hydroxide are reported. The acid activation causes a reduction in the number of cation exchange sides and, hence improves the exfoliation of the silicate sheets at higher pH values. The basal spacing increases significantly from 1.54 to 3.80 nm, and is related to the acid activation extent. The acid activated clays with acid/clay ratios above 0.2 intercalated significant amounts of C16TMA cations with a basal spacing of 3.8 nm compared to the non acid activated montmorillonite with a basal spacing of 2.10 nm. The 13C CP/MAS NMR indicates that the intercalated surfactants exhibit a significant degree of gauche conformation in the acid-activated clays. According to in-situ powder XRD, an increase of the basal spacing to 4.08 nm is observed at intermediate temperatures of 50-150 degrees C for organoclay with basal spacing of 3.80 nm, at higher temperatures above 300 degrees C, the decomposition of the surfactant occurs and the basal spacing decreases to a value of about 1.4 nm, with the persistence of a reflection at 3.8 nm for clay at a higher acid/clay ratio of 0.5.     

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.     

Organic Pillared Clays

Commonly used organophilic clays are modified by alkylammonium cations which hold apart the aluminosilicate layers permanently. The cations fill the interlayer space and are contemplated as flexible pillars, resulting from the mobility of the alkyl chains. Therefore, the interlayer distance varies depending on the layer charge and on the alkyl chain length. Contrary to these cations, rigid pillaring cations guarantee a constant interlayer distance without occupying the interlayer by themselves and show special adsorption properties such as hydrophilic behavior contrary to the generally hydrophobic ones. Smectites were modified by flexible organic cations, e.g., dimethyldioctadecylammonium, and by rigid ones, e.g., tetraphenylphosphonium. Their adsorption properties are compared. Our investigations showed improved adsorption properties for rigid organic cations on smectites using 2-chlorophenol as pollutant. Best adsorption results are achieved using pillaring cations in combination with low charged smectites, especially at low pollutant concentrations. The properties of organic modified smectites are discussed by a pollution intercalation model. The intercalation process of an organic pollutant into an organic modified smectite is expressed by a two-step Born-Haber cycle process: (i) the formation of an adsorbing position by layer expansion and (ii) the occupation of the adsorbing position by the pollutant. The first step of the formation of the adsorbing position is an endothermal transition state which lowers the total intercalation energy and therefore worsens the adsorption behavior. Thus, an already expanded organophilic smectite will show improved adsorption behavior. The formed adsorbing position state on organic modified smectites is comparable to the pillared state of inorganic pillared clays. Copyright 2001 Academic Press.     

Preparation and characterization of zwitterionic surfactant-modified montmorillonites

A series of zwitterionic surfactant-modified montmorillonites (ZSMMs) were synthesized using montmorillonite and three zwitterionic surfactants with different alkyl chain lengths at different concentrations [0.2-4.0 cation exchange capacity (CEC)]. These ZSMMs were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis and differential thermo-gravimetric (TG/DTG) analyses. The zwitterionic surfactant could be intercalated into the interlayer spaces of montmorillonites and causing interlayer space-swelling. From XRD measurements, the amount of the surfactants loaded and the basal spacing increased with surfactant concentration and alkyl chain length. One endothermic DTG peak occurred at ~390 °C, which was assigned to the decomposition of the zwitterionic surfactant on the organo-montmorillonites from 0.2 to 0.6 CEC. When the surfactant loading was increased, a new endothermic peak appeared at ~340 °C. From the microstructures of these ZSMMs, the mechanism of zwitterionic surfactant adsorption was proposed. At relatively low loadings of the zwitterionic surfactant, most of surfactants enter the spacing by an ion-exchange mechanism and are adsorbed onto the interlayer cation sites. When the concentration of the zwitterionic surfactant exceeds the CEC of montmorillonite, the surfactant molecules then adhere to the surface-adsorbed surfactant. Some surfactants enter the interlayers, whereas the others are attached to the clay surface. When the concentration of surfactant increases further beyond 2.0 CEC, the surfactants may occupy the inter-particle space within the house-of-cards aggregate structure.     

Adsorption of ammonia on graphite oxide/aluminium polycation and graphite oxide/zirconium-aluminium polyoxycation composites

Graphite oxide (GO) synthesized from commercial graphite was modified with aluminium or zirconium-aluminium polyoxycations and then calcined at 350 degrees C. On the samples obtained adsorption of ammonia from moist air was investigated. The surface of materials before and after exposure to ammonia was characterized using adsorption of nitrogen, XRD, SEM, FTIR, TA, CHN analysis, and potentiometric titration. The results showed that in spite of the fact that graphite composites/pillared graphites (PG) have Keggin-like ions located between the layers, that space blocked for nitrogen molecules used to determine the specific surface area. During calcinations, the deflagration of layers occurred as a result of decomposition of epoxy groups. This results in formation of disordered graphitic carbons with some mesoporosity. Even though these materials were not porous, the significant amount of ammonia was retained on the surface. Since ammonia molecule is able to specifically interact with oxygen groups of graphite oxide and Br?nsted centers of inorganic pillars, it is likely intercalated between the composite layers. While the best performance was found for GO modified with aluminium-zirconium species, after calcinations the samples containing Keggin Al(13) like cations revealed the high capacity which is linked to the high acidity of incorporated inorganic compounds.     

氧化铝柱层状铌酸盐的制备

本文以HNb~3O~8为例, 进一步探讨了用分步交换法来制备氧化铝柱层状金属氧化物的可行性。首次成功地将[Al~13O~4(OH)~24(H~2O)~12]^7+Keggin离子交换进入到层状金属铌酸(HNb~3O~8)的层间。通过焙烧, 制备了首例以氧化铝为柱的层状金属铌酸盐。该化合物具有很高的热稳定性(>700℃)和比较大的层间距(d=1.18nm,700℃), 讨论了不同层板性质对产物结构和性能的影响。     

XRD study of the dehydration and rehydration behaviour of Al-pillared smectites differing in source of charge

The swelling properties of Al-pillared clays, obtained from five different smectites, were studied using X-ray diffraction. These clays, the dioctahedral beidellite and montmorillonite and the trioctahedral saponite, hectorite and laponite differ in source of isomorphic substitution and represent a series of decreasing basicity along the siloxane plane. An Al oxyhydroxy cation was inserted between the layers to form the respective pillared clays and these clays were heated incrementally to 600°C. The XRD peaks at each stage of heating were recorded as well as the same samples subsequently wetted. Basal spacings of each clay at each stage of dehydration d rehydration indicated that the swelling of tetrahedrally substituted saponite and beidellite was indeed restricted, compared with the other three clays. This was attributed to greater basicity of the oxygen plane of beidellite and saponite due to tetrahedral substitution of Si by Al, resulting in an increase in the strength of hydrogen bonds between either water or the interlayer polyhydroxy cation and the clay.The data from the XRD analyses helped in addition, to clarify the thermal transformations of the Keggin ion itself. According to the changes in thed-spacings of the pillared clays it was concluded that the Keggin ion lost its structural water at 200°C and dehydroxylated in a range beginning at 350°C. Between 500 to 600°C this polymer cation, which is thought to form the Al₂O₃ oxide, did not rehydrate.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe authors wish to thank Laporte Industries, Inc., U.K. for the laponite sample.     

Selectivity in the conversion of n-heptane on an Al-PILC modified with Ga

This work compares the catalytic activity for the hydroisomerization and hydrocracking of n-heptane for two pillared clay materials, one with polyoxycations of Al and the other with the same cation modified by the inclusion of Ga. The conversion rate for the clay pillared with mixed cations is lower than that for the material pillared only with aluminum throughout the temperature range, which is attributable to its smaller specific surface area. However, at high temperatures the conversion rate of the material with mixed pillars continues to rise steadily, indicating a greater thermal stability. The incorporation of Ga also increases the selectivity for isomerization.     

Formation of organo-highly charged mica

The interlayer space of the highly charged synthetic Na-Mica-4 can be modified by ion-exchange reactions involving the exchange of inorganic Na(+) cations by surfactant molecules, which results in the formation of an organophilic interlayer space. The swelling and structural properties of this highly charged mica upon intercalation with n-alkylammonium (RNH(3))(+) cations with varying alkyl chain lengths (R = C12, C14, C16, and C18) have been reported. The stability, fine structure, and evolution of gaseous species from alkylammonium Mica-4 are investigated in detail by conventional thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), in situ X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (MAS NMR) techniques. The results clearly show the total adsorption of n-alkylammonium cations in the interlayer space which expands as needed to accommodate intercalated surfactants. The surfactant packing is quite ordered at room temperature, mainly involving a paraffin-type bilayer with an all-trans conformation, in agreement with the high density of the organic compounds in the interlayer space. At temperatures above 160 °C, the surfactant molecules undergo a transformation that leads to a liquid-like conformation, which results in a more disordered phase and expansion of the interlayer space.     

Use of the Second Derivative of TG Curves for Investigation of the Exchanged Interlayer Cation in Montmorillonite

Various cation-exchanged montmorillonites (Li+, Na+, Ba2+, Mg2+, Ca2+, Mn2+, Co2+, Cu2+, Ag+, Cd2+, Hg2+, Al3+, Pb2+ and NH4+) were prepared from calcium montmorillonite and their properties were studied by means of X-ray diffraction and thermal analysis. The two methods give information on the cation exchange in the interlayer space only. X-ray diffraction studies at room temperature are mainly suitable for estimation of the exchange of cations of different valencies. At 500°C, when the structure is completely collapsed, the d value of montmorillonite depends on the non-hydrated ionic radius of the interlayer cation, but the measurement interval is limited for fine interpretation. The thermoanalytical method is suitable for a better distinction of different exchangeable cations of higher hydration energy on the basis of the DTG or DDTG curve. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal transformations up to 1200 °C of Al-pillared montmorillonite precursors prepared by different OH–Al polymers

Aluminum-pillared montmorillonites are useful materials for their application as catalysts, adsorbents and ceramic composites. The precursor is a pillared montmorillonite that is not thermally stabilized. The precursor preparation methods, textural properties and catalytic activity have been extensively investigated, but comparatively, studies concerning their thermal transformations at high temperature are limited. In this work, precursors were prepared using two types of montmorillonites, Cheto (Ch) and Wyoming (W), and using two different OH–Al polymer sources: hydrolyzed (H) and commercial (C) solutions. Structural and thermal transformations of the precursors with heating up to 1200 °C were determined by X-ray diffraction and thermogravimetric analysis. Thermal analysis of these precursors below 600 °C revealed the influence of OH–Al polymers from the two solutions. The major phases developed at 1200 °C from the original montmorillonites were mullite for W and cordierite for Ch. The content of these phases depended on the aluminum in the octahedral sheet of the pristine montmorillonites. Amorphous phase, cristobalite, spinel, sapphirine and others phases were also found. The intercalation of OH–Al polymers in montmorillonites caused an increase in amorphous content after treatment at 1030 °C; however, it favored mullite development above 1100 °C. Although total aluminum content of both W and Ch precursors was similar, the transformation to mullite was directly related to the octahedral aluminum/magnesium ratio. The phase composition of the products at 1200 °C was not dependent on the type of intercalated OH–Al polymers. The increase in mullite content of the thermally treated precursors contributes to its possible application as advanced ceramic products.     

A combined study by XRD, FTIR, TG and HRTEM on the structure of delaminated Fe-intercalated/pillared clay

Fe-PILC samples were synthesized by the reaction between Na(+)- and/or Ca(2+)-montmorillonite (Mt) and base-hydrolyzed solutions of Fe(III) nitrate. Different from the known usual microporous pillared structure, a meso-microporous delaminated structure containing intercalated or pillared fragments was found in the respective resulting Fe-intercalated or -pillared clays. XRD patterns of Na(+)-Mt-based Fe-intercalated/pillared clays show one large d-spacing above 6.4 nm corresponding to the mesoporous delaminated part, whereas another d-spacing of ca. 1.5 nm was indicative of the microporous pillared part. Fe-intercalated/pillared clays based on Ca(2+)-Mt lead to similar results, but with a d-spacing less than 6 nm and a second low intense d-spacing less than 1.5 nm. In the delaminated Fe-intercalated clays, NO(-)(3) anions were retained even after thorough washing process. They play as counterions to neutralize the positive-charged iron aggregates in the delaminated structure, and can be exchanged by heteropolyanions as [PW(12)O(40)](3-). The delaminated Fe-pillared clays show good thermal stability at 500 degrees C and exhibit at this temperature dramatically higher specific surface area and porosity than the starting montmorillonites. However, calcination at a higher temperature leads to the formation of nanocrystalline hematite. Air-drying after ethanol extraction (EAD) method has an advantage over air-drying (AD) method in preserving the delaminated structure.     

The synthesis of pillared nickel-substituted saponite and its hydroisomerization activity

Nickel-substituted saponite clays (NiS) were synthesized. The pillared clays notedPNiS were prepared from the NiS intercalated with large inorganic cations such as [Al_(13)O_4(OH)_(24).(H_2O)_(12)]~(7+). It is found that the pillar density is correlative with aluminium content in the tetra-hedral sheet of NiS. The results from TPR indicate that the palladium loaded on samples promotesthe reduction of the nickel ion in the octahedral sheet. The pillared clays impregnated with Pd~(2+)noted PdPNiS show excellent hydroisomerization property which is much better than that of nickelsubstituted mica-montmorillonite pillared with silicon oxide oligomer noted PdPSMM. The hexaneconversion increases with the content of aluminium ion in the tetrahedral sheet, whereas the changeof the selectivity of isomerization is not obvious.     

The influence of alkyl chain length on surfactant distribution within organo-montmorillonites and their thermal stability

Organically modified clay minerals with high thermal stability are critical for synthesis and processing of clay-based nanocomposites. Two series of organo-montmorillonites have been synthesized using surfactants with different alkyl chain length. The organo-montmorillonites were characterized by X-ray diffraction and differential thermogravimetry, combining with molecule modelling. For surfactant with relatively short alkyl chain, the resultant organo-montmorillonite displays a small maximum basal spacing (ca. 1.5?nm) and most surfactants intercalate into montmorillonite interlayer spaces as cations with a small amount of surfactant molecules loaded in the interparticle pores with ??house-of-cards?? structure. However, for surfactant with relatively long alkyl chain, the resultant organo-montmorillonite displays a large maximum basal spacing (ca. 4.1?nm) and the loaded surfactants exist in three formats: intercalated surfactant cations, intercalated surfactant molecules (ionic pairs), and surfactant molecules in interparticle pores. The surfactant molecules (ionic pairs) in interparticle pores and interlayer spaces will be evaporated around the evaporation temperature of the neat surfactant while the intercalated surfactant cations will be evaporated/decomposed at higher temperature.     

过氧杂多阴离子型层柱化合物的合成、表征及催化活性

通过离子交换法,将含Zr过渡金属离子1,3取代钨硅、钨磷过氧杂多酸盐嵌入Zn2Al类水滑石中,获得了层柱化合物,并用XRD,IR,UV等手段对产物的结构进行了表征.结果表明过氧杂多阴离子进入水滑石层间后,水滑石的层间距从0.92增大到1.47 nm,且过氧链没被破坏.层柱化合物在酯化反应中显示优良的催化性能.     

Preparation and Characterization of TiO2-pillared Layered HNb3O8

IntroductionThelayeredcompoundssuchassmectiteclays,me-tallicphosphatesandtransitionmetaloxidespillaredwithinorganicoxideshavebeenattractingmoreandmoreattentionfrombothacademicandindustrialfieldsduetotheirpotentialapplicationsinadsorption,separa-tion,conductionandparticularlycatalysis.1-7NiobatessuchasKNb3O8andK4Nb6O17,andthecorrespondingprotonicoxides,HNb3O8andH4Nb6O17,aremembersofthefamilyoflayeredtransitionmetaloxidesbasedonoctahedralframeworkstructure,inwhichK+orH+liesbetweenlayersbuil…     

Synthesis and Characterizations of Hydroxy-aluminum Cross-Linked Montmorillonite

Cross-linked montmorillonite was prepared by reacting homoionic sodium form of bentonite (Na-M) from Istenmezeje (Hungary) with high molecular weight polyhydroxy-aluminum complex. The complex was prepared by controlled hydrolysis of alumina macrocation. The intercalated clay (Na-Al-M) was thermally treated to convert the hydroxy cations to oxide pillars. The pillared products were characterized by X-ray powder diffraction (XRD), Fourie transform infrared spectroscopy (FTIR), (thermogravimetry (TG), differential thermal analysis (DTA) and thermal analysis-mass spectrometry (TA-MS) methods. The specific surface area as well as pore size and pore structure distribution of samples were measured by nitrogen, water and carbon tetrachloride adsorption, and the heat of immersion was also determined. The pillared products were characterized by d(001) reflections of 19 Å, which is stable even at 500°C. The interaction of polymer alumina caused several changes in the obtained FTIR spectra due to the formation of different new bonds. The rate of dehydroxylation of the pillared product is very moderate, the water release occurred in different temperature ranges according to TA-MS results. Dehydration starts at interfaces and at the wall of pores, occurring nearly with uniform rate at 250-500°C. DTA curve indicates the formation of a new phase at 950°C. The obtained surface area of the pillared product by nitrogen adsorption becomes larger (208 m2 g-1) with respect to the non pillared clay, which decreases less than 10% upto 700°C. The pillared sample has a definite pore structure, the quantity of micropores (0-40 Å) decreased with increasing of macropores (>1000 Å). The obtained domestic pillared montmorillonite possesses a high degree of thermal stability and may be used as adsorbent.     

Tailoring micropore dimensions in pillared clays for enhanced gas adsorption

A systematic investigation has been undertaken for tailoring the micropore structure of the pillared clay. Besides the type of metal oxide (e.g. Al₂O₃ vs. ZrO₂) being used as the pillars, the important factors for determining the micropore structure are OH/Al ratio (for Al₂O₃-pillared clay), calcination temperature and the starting clay. The effect of the cation exchange capacity (CEC) of the clay on the microporous structure (and consequently the adsorption properties) is reported for the first time. Two clays with widely different CECs are used: Arizona montmorillonite (CEC = 1.40 mequiv./g) and Wyoming montmorillonite (CEC = 0.76 mequiv./g). The interlayer spacings of the pillared clays from these different clays are essentially the same, since the interlayer spacing is controlled by the sizes of the oligomers that intercalate between the clay layers. However, the pillar density in the pillared clay is substantially higher with a high CEC in the starting clay, and is shown to be approximately proportional to the CEC. Consequently, the interpillar spacing is substantially lower resulting from the higher CEC. The CH₄ adsorption on the pillared clay is nearly doubled by the smaller interpillar spacing, due to the back-to-back overlapping potential in the micropores. The N₂ adsorption was not significantly influenced because of its low polarizability (hence low inductive potential). Increasing the calcination temperature of the Al₂O₃-pillared clay from 400°C to 600°C can decrease the interlayer spacing, but only by 1 (from 8.7 to 7.7 ). The CH₄/N₂ adsorption ratio of 2.35 is reached on the Al₂O₃-pillared Arizona clay that is calcined at 600°C. Finally, the surface and pore volume are influenced by the OH/Al ratio (or pH) during pillaring, since this ratio determines the size and charge of the oligomers. A peak surface area is reached at OH/Al = 2.2.     

Thermal behaviour of montmorillonite pillared with different metal oxides

Natural montmorillonite was pillared by various polyhydroxy cations. The resulting pillared layer clays (PILCs) were characterized by X-ray fluorescence, X-ray diffraction (XRD) and infrared (IR) spectroscopies. The thermal behaviour of Al-PILC was investigated in detail by a combonation of XRD, derivatography IR spectroscopy and a comparison to natural montmorillonite is given. It was found that thermal stability of Al-PILC is lower than that of natural montmorillonite. However, heat treatment in the stability region results in significant sintering of natural montmorillonite, while the interlayer spacing of Al-PILC is hardly affected.