Influence of swelling on reaction efficiency in intercalated clay minerals. 2. Pillared clays

Methods for intercalating thermally stable, polynuclear hydroxy metal cations and/or metal cluster cations in smectite clays have been developed in recent years as a means of keeping separate the silicate layers in the absence of a swelling solvent. Since the pillaring cations are space filling, the interlamellar reaction space will be broken up into an interconnected set of channels through which a diffusing species can migrate. In this paper, a lattice model is designed to determine how different spatial distributions of pillaring agents and different interlamellar spacings can influence the efficiency of reaction between a fixed target molecule and a diffusing coreactant. The authors study two regular distributions of pillaring cations and calculate the mean reaction time (as calibrated by the mean walklength ) of the diffusing coreactant as a function of the separation between silicate layers. All other factors being held constant, they find a significant increase in the reaction efficiency with increase in the number of channels available to the coreactant. They also find that for each distribution there is a decrease in reaction efficiency as one increases the interlayer spacing, with the surprising result that for large arrays the addition of one or two layers above the basal plane (where the target molecule is anchored at the centrosymmetric site) leads to essentially the same relative changes in the reaction efficiency regardless of the spatial distribution considered.