ZIF-8 Membrane Separation Performance Tuning by Vapor Phase Ligand Treatment

Vapor phase ligand treatment (VPLT) of 2-aminobenzimidazole (2abIm) for 2-methylimidazole (2mIm) in ZIF-8 membranes prepared by two different methods (LIPS: ligand induced permselectivation and RTD: rapid thermal deposition) results in a notable shift of the molecular level cut-off to smaller molecules establishing selectivity improvements from ca. 1.8 to 5 for O₂ /N₂ ; 2.2 to 32 for CO₂ /CH₄ ; 2.4 to 24 for CO₂ /N₂ ; 4.8 to 140 for H₂ /CH₄ and 5.2 to 126 for H₂ /N₂ . Stable (based on a one-week test) oxygen-selective air separation performance at ambient temperature, 7 bar(a) feed, and 1 bar(a) sweep-free permeate with a mixture separation factor of 4.5 and oxygen flux of 2.6×10^-3 mol m^-2 s^-1 is established. LIPS and RTD membranes exhibit fast and gradual evolution upon a 2abIm-VPLT, respectively, reflecting differences in their thickness and microstructure. Functional reversibility is demonstrated by showing that the original permeation properties of the VPLT-LIPS membranes can be recovered upon 2mIm-VPLT.