Realizing the Direct Synthesis of High Silica IWS Zeolite with Improved Hydrothermal Stability

Direct synthesis of germanosilicate zeolites with low Ge content and improved hydrothermal stability is a great challenge. Herein, we successfully achieve the direct synthesis of IWS zeolite with a Si/Ge ratio higher than 4 for the first time. High silica IWS zeolites can be prepared in a wide range of Si/Ge ratios (4-16) by utilizing bulky 1,3-bis(1-adamantyl)-imidazolium (BAdaI⁺) as an efficient organic structure-directing agent from the concentrated synthesis gel under fluoride conditions. It is proven by a series of characterizations that Ge atoms preferentially occupy the double-four-ring (D4R) units. Theoretical calculations reveal the preferential interactions of guest organic structure-directing agents (OSDAs) and host IWS zeolites with different Si/Ge ratios. The introduction of more Ge atoms cannot improve the host-guest interaction when the BAdaI⁺ molecule is accommodated within the nanopores of IWS zeolite compared to other OSDAs. The obtained IWS zeolite shows an extremely high specific surface area (905 m²/g) and pore volume (1.31 cm³/g). Due to the low Ge content, IWS zeolite exhibits outstanding hydrothermal stability and experiences high temperature steam heating with no loss of crystallinity and only a slight loss of microporosity.