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Elucidating Poisson-Like Anisotropic Deformation in Flexible MOFs for Precision C2 Hydrocarbon/CO2 Sieving via
Sen Liu1, Maohuai Wang1, Yang Shao2
1College of Science, China University of Petroleum (East China), Qingdao, People's Republic of China.
Abstract:
Precise kinetic separation of light hydrocarbons (C2H2, C2H4, C2H6) and CO2 remains challenging due to their overlapping kinetic diameters and subtle host-guest interactions. Here, we rationally functionalized a series of flexible metal-organic frameworks, TYUT-18-X (X = -H, -OH, -NH2, -NO2, -CH3, and -CF3), establishing an efficient platform for dynamic molecular sieving. Combining multiscale simulations with machine-learning interpretability analysis, we unveil an anisotropic "Poisson-like" framework deformation during guest diffusion. This synchronized expansion-contraction along distinct crystallographic axes functions as a dynamic molecular gate, dramatically amplifying kinetic selectivity. Specifically, ligand functionalization effectively tailors diffusion barriers: in TYUT-18-CF3, the barrier reaches 176.43 kJ mol-1 for C2H6 versus 110.81 kJ mol-1 for C2H2, yielding an exceptional theoretical barrier-based selectivity of 3.18 × 1011 and a dynamic diffusivity ratio (DC2H2/DC2H6) of 3.8 × 102 from finite-temperature MD. Furthermore, SHAP analysis identifies the localized pore aperture and functional moiety as the governing descriptors dictating this dynamic sieving effect. This work highlights high-performance candidates for C2Hn/CO2 separations and introduces a general paradigm for programming guest-responsive structural dynamics in flexible porous materials.
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