Inorganic Pillar Center-Facilitated Counterdiffusion Synthesis for Highly H₂ Perm-Selective KAUST-7 Membranes

Fluorinated metal-organic framework materials (NbOFFIVE-1-Ni, also referred to as KAUST-7) have attracted widespread attention because of their high chemical stability and thermal stability, outstanding tolerance with water and H₂S, and high CO₂-adsorption selectivity over H₂ and CH₄. KAUST-7 was expected to be a new membrane material candidate for H₂/CO₂ separation because of the hindered permeation of CO₂ resulting from the interaction between CO₂ and (NbOF₅)^2- of the KAUST-7 framework. A highly H₂ perm-selective KAUST-7 membrane was first achieved using a novel strategy of inorganic pillar center-facilitated counterdiffusion (IPCFCD) proposed by us. The IPCFCD method not only effectively avoided the corrosion of hydrofluoric acid to α-Al₂O₃ tubes in the process of preparing KAUST-7 membranes, but also better reduced grain boundary defects because of the faster nucleation rate and resultant high crystallinity. The KAUST-7 membrane exhibited a high H₂/CO₂ separation factor (SF) of 27.30 for the 1:1 H₂/CO₂ binary gas mixture with a high H₂ permeance of 5.30 × 10^-7 mol m^-2 s^-1 Pa^-1 under ambient conditions and a slight decrease of the H₂/CO₂ SF with increasing operation temperature and presence of steam. This study highlighted the importance of pre-synthesizing inorganic pillar centers (NiNbOF₅ intermediate) and the innovation of a membrane formation process for synthesizing polycrystalline KAUST-7 membranes. Most important of all, our study provided a novel approach to overcome the challenge in fabricating metal-organic framework membranes containing corrosive reactants for the corresponding supports.