Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra-Framework Anions in Pore-Space-Partitioned Metal-Organic Frameworks

Abstract

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. The effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co₃ -cpt-tph-Cl (Hcpt=4-(p-carboxyphenyl)-1,2,4-triazole, H-tph=(2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C₂ H₂ uptake capacity (200 cm³ /g at 298 K), also exhibits (desirably) the lowest CO₂ uptake and hence the highest C₂ H₂ /CO₂ selectivity. The successful boost in both C₂ H₂ capacity and IAST selectivity allows Co₃ -cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C₂ H₂ uptake and C₂ H₂ /CO₂ experimental breakthrough separation.

Keywords: acetylene storage; cationic framework; gas separation; metal-organic framework.