Control of the Structural Charge Distribution and Hydration State upon Intercalation of CO₂ into Expansive Clay...

Numerous experimental investigations indicated that expansive clays such as montmorillonite can intercalate CO₂ preferentially into their interlayers and therefore potentially act as a material for CO₂ separation, capture, and storage. However, an understanding of the energy-structure relationship during the intercalation of CO₂ into clay interlayers remains elusive. Here, we use metadynamics molecular dynamics simulations to elucidate the energy landscape associated with CO₂ intercalation. Our free energy calculations indicate that CO₂ favorably partitions into nanoconfined water in clay interlayers from a gas phase, leading to an increase in the CO₂/H₂O ratio in clay interlayers as compared to that in bulk water. CO₂ molecules prefer to be located at the centers of charge-neutral hydrophobic siloxane rings, whereas interlayer spaces close to structural charges tend to avoid CO₂ intercalation. The structural charge distribution significantly affects the amount of CO₂ intercalated in the interlayers. These results provide a mechanistic understanding of CO₂ intercalation in clays for CO₂ separation, capture, and storage.