The adsorptive separation of molecules with very similar physical properties is always a challenging task. Reported herein is the design and tailoring of zeolite adsorbent for the precise discrimination and separation of CO2-C2H2 mixture through the pronounced trapdoor effect. Typically, Sr exchanged K-type clinoptilolite, namely Sr/K-HEU, is developed as a robust zeolite adsorbent for inverse CO2-C2H2 separation, showing the-state-of-the-art dynamic CO2/C2H2 selectivity of 48.0 and sustainable CO2 dynamic uptake of 0.96 mmol/g at the same time. The perfect recyclability and the intrinsic low-cost nature of S/Kr-HEU make it a promising candidate for practical applications. Three-dimensional electron diffraction determines the precise structure of Sr/K-HEU and density functional theory calculations reveal the intricate interplay between guest molecules and the gate-keeping extraframework cations. Briefly, extraframework Sr2+ cations from the ten-membered rings of HEU zeolites act as the molecular trapdoor, allowing the entry of CO2 molecules while excluding C2H2. This work presents a new example of molecular trapdoor in zeolite and its successful application in the challenging inverse CO2-C2H2 separation, which not only expands the scope of molecular trapdoor concept but also improves current understanding on the nature of molecular trapdoor.
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