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Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well known to be systematically correlated with the hydration free energy of the interlayer cation, in environments dominated by non-polar solvents (i.e. CO2), uptake into the interlayer is not well-understood. Using novel high pressure capabilities, we investigated the interaction of dry super-critical CO2 with Na(+)-, NH4(+)-, and Cs(+)-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H2O, and that cation solvation energies in CO2 suggest a stronger interaction with Na(+), both the NH4(+)- and Cs(+)-clays readily absorbed CO2 and expanded while the Na(+)-clay did not. The apparent inertness of the Na(+)-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na(+)-clay, but little or no energy barrier for the NH4(+)- and Cs(+)-clays. Indeed, the combination of experiment and theory clearly demonstrate that CO2 intercalation of Na-montmorillonite clays is prohibited in the absence of H2O. Consequently, we have shown for the first time that in the presence of a low dielectric constant gas swelling depends more on the strength of the interaction between interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicates swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semi-permeable reactive barriers.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO₂