Bio-Inspired Investigation on Dual-Pore Synergistic Effect in Zirconium Supramolecular Framework for Ethane/Ethylene Separation.

The hierarchical organization of discrete units into higher-order architectures is essential for emergent functions. Here, we present a zirconium-based supramolecular framework (SMF), SMF-F4-BDC, and demonstrate that its crystalline assembly is critical for C2H6/C2H4 separation. Guided by an "amino acid to protein" paradigm, discrete metal-organic cages (MOCs) are assembled into an ordered SMF, giving rise to a dual-pore synergistic effect (DPSE) between intrinsic and extrinsic pores. While the pristine framework exhibits a high C2H6 uptake of 57.1 cm3·g-1 at 1 bar and 298 K, structural denaturation leads to a dramatic reduction in adsorption capacity, accompanied by a significant loss of selectivity. This stark contrast clearly demonstrates that extrinsic packing pores are indispensable for molecular recognition. These findings establish a general design principle for high-performance adsorbents based on hierarchical pore engineering.