文摘
First-principles molecular dynamics simulations were carried out to explore the mechanistic and thermodynamic ramifications of the exposure of variably hydrated Ca-rich montmorillonites to supercritical CO2 and CO2鈥揝O2 mixtures under geologic storage conditions. In sub- to single-hydrated systems (鈮?W), CO2 intercalation causes interlamellar expansion of 8鈥?2%, while systems transitioning to 2W may undergo contraction (7%) or remain almost unchanged. When compared to 2W hydration state, structural analysis of the 鈮?W systems, reveals more Ca-CO2 contacts and partial transition to vertically confined CO2 molecules. Infrared spectra and projected vibrational frequency analysis imply that intercalated Ca-bound CO2 are vibrationally constrained and contribute to the higher frequencies of the asymmetric stretch band. Reduced diffusion coefficients of intercalated H2O and CO2 (10鈥?鈥?0鈥? cm2/s) indicate that Ca-montmorillonites in 1W hydration states can be more efficient in capturing CO2. Simulations including SO2 imply that 0.66 mmol SO2/g clay can be intercalated without other significant structural changes. SO2 is likely to divert H2O away from the cations, promoting Ca-CO2 interactions and CO2 capture by further reducing CO2 diffusion (10鈥? cm2/s). Vibrational bands at 1267 or 1155 cm鈥? may be used to identify the chemical state (oxidation states +4 or +6, respectively) and the fate of sulfur contaminants.