In Situ Fabrication of Metal–Organic Framework Thin Films with Enhanced Pervaporation Performance

Abstract The intrinsic porosity in the periodic structures of metal–organic frameworks (MOFs) endows them with a great potential for membrane separation. However, facile fabrication of crystalline MOF membranes has been challenging and limited to few materials for economic and environmental considerations. Herein, a continuous Zr‐MOF thin film with a thickness of ≈180 nm has been fabricated via in situ recrystallization of MOF nanoparticles on the porous support under formic acid vapor. Owing to the inherent microporosity and the well‐established hydrophilicity during membrane fabrication, the MOF thin films exhibit excellent pervaporation performance with separation factors of 2630, 501 and fluxes of 1.45, 1.41 kg m⁻² h⁻¹) for n‐butanol dehydration and methanol/methyl tert‐butyl ether (MeOH/MTBE) separation, respectively. The structural stability of the film has been further confirmed by its steady performance in the 10‐day pervaporation test. This in situ recrystallization method induced by a trace amount of acid vapor with no extra ingredients opens a new avenue for the facile membrane fabrication of various MOF materials to feasibly realize their versatile potential as membrane materials.