A Strategy for Constructing Pore-Space-Partitioned MOFs with High Uptake Capacity for C₂ Hydrocarbons and CO₂

Introduction of pore partition agents into hexagonal channels of MIL-88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4,4'-dipyridylsulfide (dps) ligands. One third of open metal sites in the acs net are retained in pacs MOFs; two thirds are used for pore-space partition. The Co₂ V-pacs MOFs exhibit near or at record high uptake capacities for C₂ H₂ , C₂ H₄ , C₂ H₆ , and CO₂ among MOFs. The storage capacity of C₂ H₂ is 234 cm³  g^-1 (298 K) and 330 cm³  g^-1 (273 K) at 1 atm for CPM-733-dps (the Co₂ V-BDC form, BDC=1,4-benzenedicarboxylate). These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low-energy-cost adsorbent regeneration. CPM-733-dps is stable and shows no loss of C₂ H₂ adsorption capacity following multiple adsorption-desorption cycles.