Giant multistep crystalline vs. osmotic swelling of synthetic hectorite in aqueous acetonitrile

Intercalation of large organocations into 2:1 clay minerals may be hampered by two problems: on one hand, the solubility of organocations in water is limited and the resulting high selectivity for adsorption in the polar solvent may lead to non-equilibrium structures. On the other hand, the large expansion of the interlayer space will slow down kinetics of ion exchange considerably. The best workaround for these obstacles is to suspend the clay minerals in mixtures of water with more hydrophobic organic solvents that nevertheless trigger a considerable expansion of the interlayer space by swelling. This in turn fosters ion exchange. The current study, therefore, revisited pioneering work by Bradley ( 1945 ) and investigated the swelling behavior of synthetic sodium hectorite (Na-hec) as a function of the composition of the swelling solvent, a mixture of acetonitrile and water. Up to a maximum acetonitrile content of 65 vol.%, delamination by osmotic swelling occurred. At even higher acetonitrile concentrations, swelling was limited to the crystalline swelling regime where a step-like adjustment of the d value was observed. Several mixtures were identified yielding a well defined and uniform interlayer height as evidenced by rational 00 l -series with the d spacing decreasing with increasing acetonitrile content. Surprisingly, for a specific acetonitrile:water ratio even an ordered interstratification of two strictly alternating interlayer heights with distinctly different solvent compositions was observed.