Designable Synthesis of Layered Silicates and Tunable Interlayer Expanded to Zeolites.

Layered zeolitic silicates and corresponding interlayer-expanded porous materials exhibit attractive application potential in wide fields. Nonetheless, designable synthesis and structure analysis of layered silicates remain challenging. Herein, two kinds of layered silicates are synthesized using different di-quaternary ammonium-type organic structure-directing agents (OSDAs). Their crystal structures are analyzed and verified by 3D electron diffraction (3D ED) and high-resolution TEM imaging. The suitable configurations of OSDA can lead to desirable interlayer states. Additionally, two new zeolite structures both with 12-membered ring (MR) channels intersected by 8 MR channels and larger interlayer spaces are constructed from layered silicate precursors by interlayer silylation. The new zeolitic material exhibits potential application in adsorption of organic pollution and catalytic reaction. This study is expected to develop versatile ways for the design and synthesis of layered silicates even zeolites and provide references in characterizing layered materials and zeolites as well.

Directing Highly a-Axis-Oriented ZSM-5 Nanosheets with Pre-estimated Bifunctional Imidazole Cations.

An MFI-topology nanosheet zeolite with a highly a-axis-oriented structure has rarely been reported but with a great potential for industrial applications. Theoretical calculations on the interaction energies between the MFI skeleton and ionic liquid molecules indicated the possibility of preferential crystal growth along a specific direction, according to which highly a-oriented ZSM-5 nanosheets were synthesized from commercially available 1-(2-hydroxyethyl)-3-methylimidazolium and layered silicate sources. The imidazolium molecules directed the structure formation and meanwhile acted as zeolite growth modifiers to restrict the crystal growth perpendicular to the MFI bc plane, which induced unique a-axis-orientated thin sheets with ∼12 nm thickness. The a-oriented ZSM-5 exhibited more competitive propylene selectivity and longer lifetime than bulky crystals in methanol-to-propylene (MTP) reaction. This research would provide a versatile protocol for the rational design and synthesis of shape-selective zeolite catalysts with promising applications.