Fine Tuning of MOF‐505 Analogues To Reduce Low‐Pressure Methane Uptake and Enhance Methane Working Capacity

Abstract We present a crystal engineering strategy to fine tune the pore chemistry and CH 4 ‐storage performance of a family of isomorphic MOFs based upon PCN‐14. These MOFs exhibit similar pore size, pore surface, and surface area (around 3000 m 2 g −1 ) and were prepared with the goal to enhance CH 4 working capacity. [Cu 2 (L2)(H 2 O) 2 ] n (NJU‐Bai 41: NJU‐Bai for Nanjing University Bai's group), [Cu 2 (L3)(H 2 O) 2 ] n (NJU‐Bai 42), and [Cu 2 (L4)(DMF) 2 ] n (NJU‐Bai 43) were prepared and we observed that the CH 4 volumetric working capacity and volumetric uptake values are influenced by subtle changes in structure and chemistry. In particular, the CH 4 working capacity of NJU‐Bai 43 reaches 198 cm 3 (STP: 273.15 K, 1 atm) cm −3 at 298 K and 65 bar, which is amongst the highest reported for MOFs under these conditions and is much higher than the corresponding value for PCN‐14 (157 cm 3 (STP) cm −3 ).