Ionothermal Synthesis of Germanosilicate Zeolites Constructed with Double‐Four‐Ring Structure‐Building Units in the Presence of Organic Base.

The crystallization chemistry of silica‐based zeolites in ionic liquids remains highly puzzling and interesting in the field of zeolite science. Herein, we report the successful ionothermal synthesis of germanosilicate zeolites. The ionothermal templating effect with respect to the structure, alkalinity and concentration of organic additives was comparatively studied. The results showed that a small amount of organic base could effectively aid the dissolution of silica source and facilitate the crystallization of germanosilicate zeolites with ionic liquid as template. Remarkably, STW and IRR structures constructed with double‐four‐ring (D4R) structure‐building units were ionothermally prepared using 1‐ethyl/butyl‐3‐methyl imidazolium and 1‐benzyl‐3‐methyl imidazolium ionic liquids as template, respectively. Ionothermal synthesis tailored with organic base showed suitable chemistry for the formation of germanium‐containing siliceous D4R units. This finding will be helpful for the rational exploration of novel extra‐large‐pore zeolitic structures. IRResistible: Germanosilicate zeolites were ionothermally prepared in the presence of organic base, which aided the dissolution of silica source and facilitated the crystallization of STW and IRR structures with ionic liquids of different structure as template. Ionothermal chemistry was effectively tailored by using an organic base, which exhibits a remarkable capability for the formation of germanium‐containing siliceous D4R units. [ABSTRACT FROM AUTHOR]