Sub‐Nanoporous Engineered Fibrous Aerogel Molecular Sieves with Nanogating Channels for Reversible Molecular Separation

Gating molecular separation using artificial sub-nanoporous molecular sieves is highly desirable in large-scale chemical and energy processing, such as gas separation, hydrogen recovery, carbon dioxide capture, seawater desalination, etc. However, it has remained an insurmountable challenge to create such materials. Herein, a binary meso-reconstruction strategy to develop biomimetic sub-nanoporous engineered aerogel molecular sieves (NAMSs) with reversible nanogating channels is demonstrated, in which sub-1 nm pores (≈7 Å) provide coupling size-thermodynamic gated functions that enable molecule discrimination and trapping in a reversible manner. The NAMSs show polarity-reversible adsorption in which adsorbate molecules are discriminated by each gate-admission sponge-fiber molecular sieve, facilitating size/interface synergistically induced selective separation of 1,3,5-trimethyl benzene/ethylene glycol with high separation factor and fast adsorption rate. The nanogating aerogel molecular sieves with molecularly defined sub-1 nm nanoporous architecture (≈7 Å), Murray's law hierarchical channels, ultrahigh surface area (686 m2 g-1 ), and robust self-supporting characteristics define a new benchmark for both aerogels and molecular sieves, exhibiting great potential in diversified on-demand molecular separations that are prevalent in chemical, energy, and environmental processes.