Designing a MOF‐functionalized Nanofibrous Aerogel via Vapor‐Phase Synthesis

Abstract Designing 3D mechanically robust and high‐surface‐area substrates for uniform and high‐density deposition of metal–organic frameworks (MOFs) provide a promising strategy to enhance surface accessibility and application of these highly functional materials. Nanofibrous aerogel (NFA) with its highly porous self‐supported structure composed of interconnected nanofibrous network offers an ideal platform in this regard. Herein, a facile one‐pot strategy is introduced, which utilizes direct deposition of MOF on the nanofibrous surface of the NFAs. NFAs are synthesized using electrospun polyacrylonitrile/polyvinylpyrrolidone (PAN/PVP) polymer nanofibers containing zinc acetate (Zn(Ac) 2 ), which are subjected to freeze drying and thermal treatment. The latter converts Zn(Ac) 2 to zinc oxide (ZnO), providing the sites for MOF growth while also adding mechanical integrity to the NFAs through cyclization of the PAN. Exposure of the NFA to the vapor‐phase of organic ligand, 2‐methylimidazole (2‐MeIm) enables in situ growth of zeolitic imidazolate framework‐8 (ZIF‐8) MOF on the NFA. ZIF‐8 loading on the NFAs is further improved by more than tenfold by synthesizing ZnO nanorods/protrusions on the nanofibers, which enables more sites for MOF growth. These findings underscore a significant advancement in designing MOF‐based hybrid aerogels, offering a streamlined approach for their use in diverse applications, from catalysis to sensing and water purification.