Investigation on the Selective <scp> SF ₆ </scp> / <scp> N ₂ </scp> Adsorption Performance of Interlayer‐Slipped <scp>2D</scp> Covalent Organic Frameworks

ABSTRACT This study systematically explores the regulation mechanism of SF 6 /N 2 adsorption performance and selectivity by constructing two‐dimensional covalent organic frameworks (COF‐120) with varying interlayer‐slipped structures. Grand canonical Monte Carlo (GCMC) simulations conducted at 298 K and 100 kPa reveal that the slipped stacking configuration, such as AB stacking, significantly enhances the SF 6 uptake. The adsorption capacity increases from 1.281 mmol/g in pristine COF‐120 to 7.752 mmol/g in the slipped structure, representing more than a sixfold improvement. Meanwhile, the SF 6 /N 2 selectivity increases from 7.034 to 40.56, indicating excellent separation performance. Thermodynamic analysis shows that SF 6 adsorption is primarily thermodynamically driven, which aligns with the observed adsorption trend. In contrast, interlayer slipping has a negligible effect on N 2 uptake, further enhancing the selectivity toward SF 6 . Radial distribution functions and two‐dimensional density maps illustrate that the slipped stacking alters the pore morphology and redistributes adsorption sites, leading to multilayer adsorption of SF 6 and promoting a more uniform molecular distribution with stronger interactions within the framework. These results confirm that interlayer slipping in two‐dimensional COFs is an effective structural modulation strategy, significantly improving gas adsorption performance and offering theoretical insights for the design of high‐efficiency greenhouse gas separation materials.