Pillared layer clay

Pillared clays, layered silicates whose sheets have been permanently propped open by thermally stable molecular props, were used as templates to load various organic precursors.The pore diameters of resulting carbon materials range from 8 to 22 A, and the mass fractal dimension varies from 2.5 to 2.9, which are accessible to lithium ions when the intercalation process takes place in a lithium secondary battery. An approach to pyrolyse aromatic hydrocarbons such as pyrene within a pillared clay was also reported, in which the pillared clay serves two functions.It acts as the inorganic template around which the carbon can be formed, and it also functions as an acid catalyst to promote condensation of the aromatics similar to the Scholl reaction. The resulting carbon materials have pore sizes from 15 to 50... 

The coke deposition on Ti- and Al-PILC was investigated by Maes and Vansant [59,60]. The reported techniques were in fact unsuccessful in achieving a controlled pore size modification, but the obtained results can function as a basis for further investigations and optimization. The pillared clay layers were found to be too rigid, preventing the bulky PVA molecules to penetrate the pores. Therefore, PVA adsorption mainly takes place on the external surface of... 

Alkvl Azides from Alkyl Bromides and Sodium Azide General procedure for the synthesis of alkyl azides. In a typical experiment, benzyl bromide (360 mg, 2.1 mmol) in petroleum ether (3 mL) and sodium azide (180 mg, 2.76 mmol) in water (3 mL) are admixed in a round-bottomed flask. To this stirred solution, pillared clay (100 mg) is added and the reaction mixture is refluxed with constant stirring at 90-100 C until all the starting material is consumed, as obsen/ed by thin layer chromatographv using pure hexane as solvent. The reaction is quenched with water and the product extracted into ether. The ether extracts are washed with water and the organic layer dried over sodium sulfate. The removal of solvent under reduced pressure affords the pure alkyl azides as confirmed by the spectral analysis. ... 

Pillared clays (MELS) are aLso covered in this review. MELS have three-dimensional network structure like zeolites, and, unlike clays, which have two-dimensional layered structures, pillared cationic and anionic clays have been studied. Phthalocyanins intercalated in anionic clays have given interesting results for wastewater purification (Vaccari, 1998). 

Similar methods of encapsulation are also observed in pillared clays, which were also introduced as catalysts as long ago as the early 1980s. The field has been thoroughly reviewed up to 2000 [65], Layered double hydroxide structures have also been used for the entrapment of metal coordination compounds [66],... 

The pillared clays were also characterized by XRD. The [001] reflection characteristic of the expansion of the clay Is due to Insertion of the hydroxyalumlnum polycations between the clay layers. In Figure 5 the traces of the [001] reflection are shown... 

Use of organic templates In the current preparation of a new series of microporous crystals, organic templates are often used. Organic chemicals are also used in the preparation of pillared clays to control the pore sizes and the porosity as follows The interlayer cations of silicate layer are exchanged with positively charged sol particles, and then a part of the sols are exchanged with organic template cations such as octadecyl trimethyl ammonium (OTMA). 

The acidic properties of alumina pillared clays have been extensively studied from the interest in using the pillared clays as cracking catalysts [21-24]. Sakurai et al. [25] studied the acidic properties of the alumina pillared clays with different kinds of silicate layers and concluded that the alumina pillars between the silicate layers did not have any acidity and that the role played by the pillars was only to make the original acidity of the silicate interlayers more easily accessible through opening the interlayer spaces. 

Lithium introduced in the structure of the clay allows to control the density of the pillars and the strength of interaction between the pillar and the clay layer. At low calcination temperature, the interlayer distances and the surface area increased. The thermal stability of the clay, calcined at temperature higher than 400°C, drastically decreases. 

A small increase of the (d 001) basal spacing is observed for the Li containing Zr pillared clays. However, the thermal stability of these solids drastically decrease. At high temperature, the collapse of the strucutre is also supported by the decrease of the surface area which is, at 700°C, almost identical to those measured for the montmorillonite. Different hypothesis may be proposed to explain the increase of the interlayer distance at low temperature (i) a better polymerization of the intercalated complex (ii) a modification of the distribution of the pillars (iii) a lower interaction between the pillar and the silica layer. The first hypothesis may easily be eliminated since the small variation of the height of the pillars (less than 1 A) cannot be explained by structural changes of the... 

The diffusion of Li+ in the octahedral cavities of the Na+montmorillonite allows to control the density of the pillars of the Zr pillared montmorillonite. The solids, stable up to 300°C, have larger surface area basal distancy than the pure Zir montmorillonite. The distance between the pillars increases while the interaction strength between the pillars and the clay layer decreases. 

Figure 1 shows the ammonia TPD spectra obtained with Al-mont and Al-sapo calcined at 400°C. Al-sapo was more acidic than Al-mont. It is generally assumed that the acid sites on pillared clays are attributable either to the silicate layer of clays or to the pillars. It was shown previously [8,9] that the acidity increased with increasing number of pillars. The number of pillars, however, cannot serve to elucidate the difference in acidity between Al-mont and Al-sapo because more acidic Al-sapo has smaller number of pillars than Al-mont, being 2.20 and 3.3 imiol/g, respectively. Many investigators have proposed... 

Clays-pillared clays or organoclays 2D, 3D varies Purification and ion exchange by surfactants of naturally occurring products or synthesis Weeks to months Interlayer distance could be varied and precisely determined X-ray diffraction measurements particles could be grown in situ or incorporated between layers complex supramolecular architecture was possible 478,480,482... 

Reduction of metal oxides, intercalated between the 72 clay layers (pillared clays), led to metal-intercalated clay nanocomposites... 

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

We also found that surfactant treatment did not work on Al- and LaAl-PILBs. The pillar precursors of these pillared clays hold the clay layers strongly. In contrast, the forces in the modified sol particles to hold the clay layer are weak, allowing radical change in the framework when the wet cake of the sample is subjected to SCD or surfactant treatment. This unique property leads to various derivative materials of different pore structures. 

When pillared smectites without tetrahedral substitution are calcined, there is no reaction between the pillars and the smectite layers. By contrast, a considerable structural transformation occurs when pillared beidellite is calcined, which has been interpreted as the growth of a three-dimensional quasi-zeolitic framework between the two-dimensional clay layers. The acidic properties of the product are comparable with those of zeolite Y and much more pronounced than those of calcined pillared smectites without tetrahedral substitution. 

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