Interactions of monovalent organic cations with pillared clays

Interactions between an acid-activated pillared clay and several organic cations including dyes (methylene blue, MB; crystal violet, CV; acriflavin, AF) and benzyl derivatives (benzyltrimethylammonium, BTMA; benzyltriethylammonium, BTEA) were studied by adsorption measurements and X- ray diffraction. When the dyes were adsorbed from low ionic strength solutions, adsorption was irreversible but saturated at levels below the cation exchange capacity (CEC) of the clay (0.6 meq/g). The difference with CEC value was largest for CV. This mode of adsorption was interpreted in terms of interlayer adsorption with steric hindrance in the pillared galleries. On the other hand, when the dyes were adsorbed from high ionic strength solutions, adsorption levels well beyond the CEC of the clay could be reached, in particular for MB and CV. This was interpreted in terms of a second adsorption mode, involving formation of molecular aggregates on the outer surface of the clay, as evidenced by X-ray diffraction. The behavior of the cationic benzyl derivatives was markedly different, with an adsorption level always below the CEC and a decrease of adsorption as the ionic strength was increased, as expected for non-complex-forming cations.