Pillared MFI Zeolite Nanosheets of a Single-Unit-Cell Thickness

Zeolite MFI nanosheets of 2-nm thickness have been hydrothermally synthesized via cooperative assembly between silica and an organic surfactant, which is functionalized with a diquaternary ammonium group. The zeolite nanosheets have been further assembled into their ordered multilamellar mesostructure through hydrophobic interactions between the surfactant tails located outside the zeolite nanosheet. This assembly process involves successive transformations from an initially hexagonal mesophase to a multilamellar mesophase without crystallinity and then to a lamellar mesophase with a crystalline zeolite framework. The mesopore volume in the interlamellar space could be retained by supporting the zeolite nanosheets with silica pillars, as in pillared clays, even after surfactant removal by calcination. The mesopore diameters could be controlled according to the surfactant tail lengths. Due to the interlamellar structural coherence, the hierarchically mesoporous/microporous zeolite could exhibit small-angle X-ray diffraction peaks up to the fourth-order reflections corresponding to the interlayer distance. In addition, an Ar adsorption analysis and transmission electron microscopic investigation indicated that the pillars were highly likely to be built with an MFI structure. The present approach using a zeolite structure-directing functional group contained in a surfactant would be suitable for the synthesis of other related nanomorphous zeolites in the future.