Clay complexes organic cations

Adsorption of Metal Ions and Ligands. The sohd—solution interface is of greatest importance in regulating the concentration of aquatic solutes and pollutants. Suspended inorganic and organic particles and biomass, sediments, soils, and minerals, eg, in aquifers and infiltration systems, act as adsorbents. The reactions occurring at interfaces can be described with the help of surface-chemical theories (surface complex formation) (25). The adsorption of polar substances, eg, metal cations, M, anions. A, and weak acids, HA, on hydrous oxide, clay, or organically coated surfaces may be described in terms of surface-coordination reactions ... 

The catalytic application of clays is related closely to their swelling properties. Appropriate swelling enables the reactant to enter the interlamellar region. The ion exchange is usually performed in aquatic media because the swelling of clays in organic solvents, and thus the expansion of the interlayer space, is limited and it makes it difficult for a bulky metal complex to penetrate between the layers. Nonaqueous intercalation of montmorillonite with a water-sensitive multinuclear manganese complex was achieved, however, with the use of nitromethane as solvent.139 The complex cation is intercalated parallel to the sheets. 

When organic cations (e.g., cationic tensides) are employed, clay organo-complexes are formed, which can be used in organic solvents. A Pd-hexadecy-lammonium montmorillonite catalyst was prepared by the reduction of Pd(OAc)2 by ethanol in the interlamellar space. At small ethanol concentrations in toluene, selective interlamellar sorption of ethanol was established consequently, the reduction also occurred only in the interlamellar space.160 The catalyst was used for the hydrogenation of alkenes.161... 

Clay minerals or phyllosilicates are lamellar natural and synthetic materials with high surface area, cation exchange and swelling properties, exfoliation ability, variable surface charge density and hydrophobic/hydrophilic character [85], They are good host structures for intercalation or adsorption of organic molecules and macromolecules, particularly proteins. On the basis of the natural adsorption of proteins by clay minerals and various clay complexes that occurs in soils, many authors have investigated the use of clay and clay-derived materials as matrices for the immobilization of enzymes, either for environmental chemistry purpose or in the chemical and material industries. 

In order to improve the textural properties of particle-clay nanohybrids, bulky organic cations are intercalated as a kind of template into particle-intercalated clays before stabilization procedures. Intercalation of the organic cations results in the removal of some of the intercalated nanoparticles and/or in their rearrangement. Subsequent calcination leads to formation of additional pore space that is highly correlated to the geometry and size of the templates. This technique allows fine tuning of textural properties in the preparation of particle-clay nanohybrids. The clay nanohybrids intercalated with metals, oxides, and complexes have a broad range of applications. In particular, metal oxide particle-pillared clays have excellent potentials as catalysts, catalyst supports, selective adsorbents, etc. " ... 

The radioactive chromium (51Cr) found in Columbia River sediments contaminated with effluent from a nuclear reactor facility was not released by the major cations of sea water or by 0.05 M CuS0424 . The results of previous work in this laboratory (New England Aquarium) showed that of the silver(I) and cadmium(II) adsorbed on the clay minerals kaolin and montmorillonite, in essentially deionized water, less than half was desorbed on mixing with sea water25 . One may postulate from results such as these that most of the heavy metals occluded within a complex organic... 

Aeration, water-holding capacity, and permeability are all improved by humus. The frequent addition of easily decomposable organic residues leads to the synthesis of complex organics (e.g., polysaccharides) that bind soil particles into aggregates. The intimate association of clay-sized particles (layer silicates) with humus via cation (e.g., calcium, magnesium, aluminum, iron) bridges also promotes aggie-... 

Clay complexes with organic cations may absorb neutral organic molecules in the interlayer space. This process is accompanied by a separation of the silicate layers and, generally, with a change of orientation of the organic cation. Thus, adsorption of benzene or chlorobenzene in pyridinium-montmorillonite changes the disposition of the pyridinium ion from parallel to normal to the silicate layers, and an increase of from 1.25 to 1.50 nm is observed. IR studies of the dichroism of specific IR absorption bands show that the pyridinium cations have their N—H groups directed to the layer surface (C2 axis perpendicular to the layers). For chlorobenzene, the molecules also adopt a perpendicular orientation but with the C—Cl bond axis (C2 axis) parallel to the layers (30). 

Clays.—The adsorption properties of clays have been extensively studied in the past and the situation up to 1976 is dealt with in van Olphen s book. A major feature of recent work has been the study of the effect on their adsorption characteristics of modification of clays by exchangeable organic cations. The earlier work of Dekany and his collaborators, outlined in a previous Report (Vol. 3, p. 147) and a publication in Hungarian, has been continued. They have been concerned mainly with the adsorption of benzene + alkane and benzene + alcohol mixtures on montmorillonites and kaolinites treated to varying extents with hexadecylpyridinium chloride (HDPCl) to form HDP-complexes of known HDP-content and having a partially organophilic surface. 

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