Electron Diffraction on Flash-Frozen Cowlesite Reveals the Structure of the First Two-Dimensional Natural Zeolite

• Published in: ACS central science Vol. 6; no. 9; pp. 1578 - 1586
• Main Authors: Mugnaioli, Enrico, Lanza, Arianna E, Bortolozzi, Giorgio, Righi, Lara, Merlini, Marco, Cappello, Valentina, Marini, Lara, Athanassiou, Athanassia, Gemmi, Mauro
• Format: Journal Article
• Language: English
• Published: American Chemical Society 23-09-2020
• ISSN: 2374-7943; 2374-7951
• DOI: 10.1021/acscentsci.9b01100

Cowlesite, ideally Ca6Al12Si18O60·36H2O, is to date the only natural zeolite whose structure could not be determined by X-ray methods. In this paper, we present the ab initio structure determination of this mineral obtained by three-dimensional (3D) electron diffraction data collected from single-crystal domains of a few hundreds of nanometers. The structure of cowlesite consists of an alternation of rigid zeolitic layers and low-density interlayers supported by water and cations. This makes cowlesite the only two-dimensional (2D) zeolite known in nature. When cowlesite gets in contact with a transmission electron microscope vacuum, a phase transition to a conventional 3D zeolite framework occurs in few seconds. The original cowlesite structure could be preserved only by adopting a cryo-plunging sample preparation protocol usually employed for macromolecular samples. Such a protocol allows the investigation by 3D electron diffraction of very hydrated and very beam-sensitive inorganic materials, which were previously considered intractable by transmission electron microscopy crystallographic methods.