Pillared clays, oxidation

Pillared clays are smectite minerals or iUite-smectite minerals that have been stmcturaHy modified to contain pillars of stable inorganic oxide. The pillars prop open the smectite stmcture so they have a basal space of approximately 3.0 nm. Typical metals in the pillars include Al, Zr, Ti, Ce, and Fe, and these materials are used in catalytic processes to crack heavy cmde oils (110—112). 

Tertiary butylhydroperoxide (TBHP) is a popular oxidizing agent used with certain catalysts. Because of its size, TBHP is most effective with catalysts containing large pores however, it can also be used with small-pore catalysts. Using first-row transition metals, Cr and V, impregnated into pillared clays, TBHP converts alcohols to ketones, epoxidizes alkenes, and oxidizes allylic and benzylic positions to ketones.83-87... 

N anomaterials have been around for hundreds of years and are typically defined as particles of size ranging from 1 to 100 nm in at least one dimension. The inorganic nanomaterial catalysts discussed here are manganese oxides and titanium dioxide. Outside the scope of this chapter are polymers, pillared clays, coordination compounds, and inorganic-organic hybrid materials such as metal-organic frameworks. 

Keywords Catalytic wet hydrogen peroxide oxidation, Iron, p-Coumaric acid, Pillared clay, Olive oil mill effluents. 

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... 

Fig. 4. Acid strength distribution for the clays pillared with oxide sols heated at 500°C O, TiOo F3, Si02 TiO A. Si02-Feo03 pillared clays.

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

Heterogeneous catalysts for liquid phase oxidations can be divided into three different categories (a) supported metals (e.g. Pd/C), (b) supported metal ions (e.g. ion exchange resins, metal ion exchanged zeolites) and (c) supported oxometal (oxidic) catalysts (e.g. Ti1v/SiOg, redox zeolites, redox pillared clays). This division of the various catalyst types will be used as a framework for the ensuing discussion. 

Redox pillared clays as shape selective oxidation catalysts... 

Such regioselectivities are unique and suggest that redox pillared clays may have broad scope and utility as selective, heterogeneous catalysts for liquid phase oxidations. Indeed, V-PILC also catalyzes the oxidation of benzyl alcohol (to a mixture of benzoic acid and benzylbenzoate) whilst a-methyl benzylalcohol is left completely untouched.71 Similarly, p-substituted benzyl alcohols are oxidized whilst o-substituted benzyl alcohols are inert.71... 

Lenoble, V., Bouras, O., Deluchat, V. et al. (2002) Arsenic adsorption onto pillared clays and iron oxides. Journal of Colloid and Interface Science, 255(1), 52-58. 

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. 

The similarities in catalytic reactivity between Cr3 53-montmorillonite and chromia supported on alumina suggest that the structure of the intercalated chromia particles may resemble the structure of the bulk oxide. In order to obtain structural information for the chromia aggregates in pillared clays, we have initiated structural studies of these materials. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy is being recognized as an effective tool for determining the local structure of a variety of materials. The basic principles and utility of this technique have been discussed elsewhere (18.). ... 

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