Nanoscale Understanding on CO₂ Diffusion and Adsorption in Clay Matrix Nanopores: Implications for Carbon Geosequestration

Carbon capture and storage (CCS) in subsurface reservoirs represents a highly promising and viable strategy for mitigating global carbon emissions. In the context of CCS implementation, it is particularly crucial to understand the complex molecular diffusive and adsorptive behaviors of anthropogenic carbon dioxide (CO₂) in the subsurface at the nanoscale. Yet, conventional molecular models typically represent only single-slit pores and overlook the complexity of interconnected nanopores. In this work, finite kaolinite lamellar assemblages with abundant nanopores (r < 2 nm) were used. Molecular dynamics simulations were performed to quantify the spatial distribution correlations, adsorption preference, diffusivity, and residence time of the CO₂ molecules in kaolinite nanopores. The movement of the CO₂ molecules primarily occurs in the central and proximity regions of the siloxane surfaces, progressing from larger to smaller nanopores. CO₂ prefers smaller nanopores over larger ones. The diffusion coefficients increase, while residence times decrease, with the pore size increasing, differing from typical slit-pore models due to the pore shape and interconnectivity. The perspectives in this study, which would be challenging in conventional slit-pore models, will facilitate our comprehension of the CO₂ molecular behaviors in the complex subsurface clay sediments for developing quantitative estimation techniques throughout the CCS project durations.