Reticular Chemistry‐Guided Topology Engineering of Pillar‐Layer Metal−Organic Frameworks for Boosting SF ₆ /N ₂ Separation

Abstract Pillar‐layered metal−organic frameworks (MOFs) hold high promise in the field of gas adsorption and separation. Capitalizing on reticular chemistry and topology‐guided pore engineering, we herein present a rare non‐interpenetrated MOF based on the pillaring of hxl layer, comprised of hexanuclear Ni 6 clusters bridged by mixed O‐ and N‐donor linkers. Notably, it features uniform triangular channels with optimal ultramicropore size and positive surface potential, constituting a molecular trap for SF 6 . By leveraging such pore characteristics, a commendable low‐pressure adsorption capacity and selectivity for SF 6 over N 2 is achieved, significantly superior to the counterparts of pillared sql ‐ and kgm ‐MOFs and on par with some leading adsorbents. A joint theoretical and crystallographic study reveals the superiority of topology‐directed pore regulation on SF 6 adsorption. Breakthrough experiments demonstrate that this MOF is capable of recovering high‐purity (>99.9%) SF 6 from binary SF 6 /N 2 mixture (10/90, v/v) at ambient conditions, attaining a record‐high productivity in a single adsorption‐desorption cycle. Moreover, excellent stability and scalable synthesis with low costs confer it with a great application prospect.