Synergistic Binding Sites in a Robust and Scalable Metal–Organic Framework for Record CH4 Capture

Abstract Effectual CH 4 reclamation from CH 4 /N 2 blends by existing physisorbents in industrialization confronts the adversity of frustrated separation performance, weak structural strength, and restricted scale‐up preparation. To solve aforesaid bottlenecks, herein, a strategy is presented to fabricate synergistic strong recognition binding sites in a robust and scalable optimum Cu(pma) 2 with ultramicroporous feature regarding superb CH 4 separation versus N 2 . By virtue of the synergistic contribution of multiple affinities accompanied by enormous potential field overlap of pore restriction, it imparts strong recognition binding toward CH 4 molecules. Equilibrium adsorption bears a record KH, CH 4 (88.2 cm 3 (STP) g −1 bar −1 ), CH 4 uptake (48.5 cm 3 (STP) g −1 bar −1 ), CH 4 stacking density (303.9 g L −1 ), separation potential (1.52 mol L −1 ) coexisting with one of the highest CH 4 /N 2 selectivity (11.5) and Q0 st, CH 4 (29.8 kJ mol −1 ) hitherto, authorizing a novel benchmark. Thermodynamically driven separation mechanisms within Cu(pma) 2 ‐established synergy of strong recognition forces are deciphered by in situ PXRD and FT‐IR combined with theoretical studies. The breakthrough effect of the highest CH 4 dynamic uptake (28.8 cm 3 (STP) g −1 ) in cooperation with exceptional recyclability and easy synthesis scalability under ambient conditions strengthened the attractiveness of Cu(pma) 2 .