Influence of downsizing of zeolite crystals on the orthorhombic ↔ monoclinic phase transition in pure silica MFI-type

•Micro- and nanosized silicalite-1 exhibit orthorhombic ↔ monoclinic phase transition.•Identification of phase transition by 29Si MAS NMR and PXRD data.•Phase transition extinction for pure silica MFI-type nanosheets.

The impact of crystal size on the transition orthorhombic ↔ monoclinic phase in MFI-type purely silica zeolites is investigated between 293 and 473 K using 29Si MAS NMR and powder X-ray diffraction. Three silicalite-1 zeolites are synthesized: a material constituted of micron-sized crystals, pseudospherical nanometer-sized crystals and hierarchical porous zeolites with a mesoporous network created by the use of a gemini-type diquaternary ammonium surfactant giving nanosheet zeolites. Our results show for the first time that the orthorhombic ↔ monoclinic phase transition already known for micron-sized particles also occurs in nanometer-sized zeolite crystals whereas our data suggest that the extreme downsizing of the zeolite crystal to one unit cell in thickness leads to an extinction of the phase transition.

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