Facile Synthesis of Ultra-microporous Pillar-Layered Metal-Organic Framework Membranes for Highly H₂-Selective...

Recently, pillar-layered MOF materials have attracted much attention and shown great potential in separation application due to their fine pore size/channel and pore surface chemistry tunability and designability. In this work, we reported an effective and universal synthesis strategy for preparing ultra-microporous Ni-based pillar-layered MOF [Ni₂(L-asp)₂(bpy)] (Ni-LAB) and [Ni₂(L-asp)₂(pz)] (Ni-LAP) (L-asp = L-aspartic acid, bpy = 4,4'-bipyridine, pz = pyrazine) membranes on a porous α-Al₂O₃ substrate with high performance and good stability by secondary growth. Through this strategy, the seed size reduction and screening engineering (SRSE) is proposed to obtain uniform sub-micron size MOF seeds by high-energy ball milling-combined solvent deposition. This strategy not only effectively addresses the issue of obtaining the uniform small seeds being significant for secondary growth but also provides an approach for the preparation of Ni-based pillar-layered MOF membranes where the freedom of synthesizing small crystals is lacking. Based on reticular chemistry, the pore size of Ni-LAB was narrowed by making use of shorter pillar ligands of pz instead of the longer pillar ligand of bpy. The prepared ultra-microporous Ni-LAP membranes exhibited a high H₂/CO₂ separation factor of 40.4 with H₂ permeance of 9.69 × 10^-8 mol m^-2 s^-1 Pa^-1 under ambient conditions and good mechanical and thermal stability. The superiority of the tunable pore structure and the remarkable stability of these MOF materials showed great potential for industrial H₂ purification. More importantly, our synthesis strategy demonstrated the generality for preparation of MOF membranes, enabling the regulation of membrane pore size and surface functional groups by reticular chemistry.