Oxides, pillaring

The formation of Si nanodot arrays on a substrate was performed by ICPRIE of Si films using self-assembled niobium oxide pillars as an etching mask. The etch rates of niobium oxide pillars and Si films, and the etch selectivity of Si films to niobium oxide were investigated by varying etch parameters in a Ch/Ar gas. The main etch parameters used in this study were the concentration of CI2 gas, coil rf power, and dc-bias to substrate. 

Figure 1(a) shows the etch rates of niobium oxide pillar and Si film, and the etch selectivity of Si to niobium oxide as a function of CI2 concentration. The etch condition was fixed at coil rf power of 500 W, dc-bias to substrate to 300 V and gas pressure of 5 mTorr. As the CI2 concentration increased, the etch rate of niobium oxide pillar gradually decreased while Si etch rate increased. It indicates that the etch mechanism of niobium oxide in Cl2/Ar gas is mainly physical sputtering. As a result, the etch selectivity of Si film to niobium oxide monotonously increased. The effect of coil rf power on the etch rate and etch selectivity was examined as shown in Fig. 1(b). As the coil rf power increased, the etch rates of niobium oxide and Si increased but the etch rate of niobium oxide showed greater increase than that of Si. It is attributed to the increase of ion density with increasing coil rf power. Figure 1 (c)... 

Fig. 1. Etch rates of niobium oxide pillar and Si film, and etch selectivity of Si to niobium oxide piUar for the variation of (a) CI2 concentration, (b) coil rf power, and (c) dc-bias voltage to susceptor...

The hydroamination of alkenes has been performed in the presence of heterogeneous acidic catalysts such as zeolites, amorphous aluminosilicates, phosphates, mesoporous oxides, pillared interlayered clays (PILCs), amorphous oxides, acid-treated sheet silicates or NafioN-H resins. They can be used either under batch conditions or in continuous operation at high temperature (above 200°C) under high pressure (above 100 bar). 

Morishige K, Hamada T. Iron oxide pillared graphite, Langmuir 2005, 21, 6277-6281. 

General procedures for the preparation of pillared clays are schematically illustrated in Fig. 1. The first and most important reaction for the introduction of pillars is ion-exchange the hydrated interlayer cations of montmorillo-nite are exchanged with precursory polynuclear metal hydroxy cations. After the ion-exchange, the montmorilIonite is separated by centrifugation and washed with water several times to remove excess hydroxy ions. The interlayered hydroxy cations are then converted into the respective oxide pillars by calcination. The precursors developed so far and the interlayer spacings of their... 

Fig. 1. Schematic illustrations of the procedures for the preparation of ceramic oxide pillared clays.

Most of the pillared structures are thermally stable up to about 500°C, and keep the specific surface area as large as 300-500 m /g. The bismuth [11] and the chromium oxides pillared clays collapse on heating to 300°C, the pillars being removed out of the interlayer spaces, although the chromium oxide with a larger basal spacing of 21 A is more thermally stable in a nitrogen atmosphere [10]. 

The acidity of the sol oxide pillared clays was also studied by a titration method with Hammett indicators [16], The acidity distributions of the three kinds of sol oxide pillared clays are shown in Fig. 4. The Ti02 pillared clay... 

In an effort to more fully elucidate the structure and reactivity of metal oxide pillared clays, we have been investigating the structure-reactivity properties of chromia-pillared derivatives (17). In the following sections, we provide an example of the structure-catalytic reactivity properties of chromia-pillared montmorillonites. Also, we report our initial efforts to structurally characterize the intercalated chromia aggregates by Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy. Unlike previously reported metal oxide pillared clays, chromia-pillared clay exhibits strong K-edge absorption and fine structure suitable for determination of metal-oxygen bond distances in the pillars. 

Many cation-exchanged clays are suitable for the production of metal-oxide-pillared clays. The hydrolysis of the cation helps the pillaring step, so, at first, the aluminum ion was applied as a pillaring agent. Later, other elements were also used, for example, zirconia chromium iron transition metal elements and some lantanoids, organometallic complexes, surfactants, and polymers. 

Aluminum oxide pillared smectites. The effect of steam deactivation (18 hr, 100% steam) of conventional Al203-pillared montmorillonite on surface area and cracking performance is shown in Table I. 

Silicon oxide / Aluminum oxide pillared smectites. Si02/Al203-pillared smectites were prepared using two different methods (6). The surface areas of the pillared products decreased with increasing Si/Al-ratio in the pillaring solution while the basal spacings were essentially independent of this ratio. 

The acidity of pillared clays has been characterized by both microcalorimetric measurements of the adsorphon of aromatic molecules and pyridine and the catalytic ethylbenzene test reaction [111]. The aromatic probe molecules used were a reactant and a product of the catalytic reaction ethylbenzene and m-diethylben-zene, respectively. In this way, only the strongest of the accessible acid sites were htrated. The heats of adsorphon of these molecules indicate that a zirconium oxide pillared clay had stronger acidity than an aluminum oxide pillared clay, whereas the pyridine results were equal for both samples. 

Both natural clays and their alnminium oxide pillared analogues have also been tested for the catalytic cracking of polyethylene [49-51]. The clays investigated include mont-morillonite and saponite. They possess a layered structure which can be converted into a two-dimensional network of interconnected micropores by intercalation of molecular moieties. In the case of alnmininm pillared clays, these materials show a mild acidity... 

These clays have been hybridized with diverse structural types of components such as nanoparticles, clusters, complex compounds, polymers, molecules, and ions. Their potential apphcations are found in many fields as inorganic catalysts, adsorbents, ceramics, coatings, and even drug delivery carriers. Various preparation methods have been developed such as pillaring, intercalation, and delamination techniques. The representative examples include organic-clay hybrids," metal oxide-pillared clays, " and bioclay hybrids. ... 

The most well-known examples are aluminum oxide pillared clays, which are stable in both oxidizing and reducing atmospheres. AI2O3 pillared clays are... 

Cations based on substituted silsesquioxanes have also been intercalated [7]. On heating the ion-exchanged clay minerals water is evolved, but oxycation or oxide pillars keep the siliceous layers apart. These materials have enhanced thermal stability compared with clay minerals expanded with organic cations. Expanded clay minerals cover at least as wide a range of accessibilities to the interlamellar micropore spaces as the zeolites, but the pore characteristics of clay minerals with inorganic pillars need more detailed investigation. 

Copper nitrate on montmorillonite (Claycop) has been used with acetic anhydride to nitrate chlorobenzene in 100% yield, giving 13 85 orthdpara isomers.249 When an iron oxide pillared clay was used, 94% para-isomer was obtained.250 Claycop and its iron analogue have been used to oxidize a pyrazoline to a pyrazole (6.47) in 64-97% yields.251... 

Selectivity in the dehydration of olefins is improved with pillared clays. Clays with aluminum oxide or mixed aluminum and iron oxide pillars converted isopropyl alcohol to propylene with more than 90% selectivity.256 A small amount of isopropyl ether was formed. When zeolite Y is used, the two products are formed in roughly equal amounts. A tantalum-pillared montmorillonite converted 1-butanol to butenes at 500°C with 100% selectivity at 41% conversion.257 The product contained a 17 20 16 mixture of 1 -butene/c/s-2-butene/fra/ s-2-butene. No butyraldehyde or butyl ether was formed. A pillared clay has been used for the alkylation of benzene with 1-dodecene without formation of dialkylated products.258 The carbonylation of styrene proceeded in 100% yield (6.50).259... 

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