Syntheses of high-silica zeolites in urea/choline chloride deep eutectic solvent

Abstract

This paper presents the first example of high-silica and siliceous zeolite synthesis in the urea/choline chloride mixture as a deep eutectic solvent (DES) using F– as the mineralizing agent. A urea/choline chloride mixture was previously used as solvent to prepare AlPO4-based microporous materials SIZ-2 and AlPO-CJ2. However, generating these materials depends on the formation of ammonium ion as a structure-directing agent (SDA) that is the side product of urea decomposition. In the present study, we show that several highly siliceous zeolites with targeted topologies (MFI, BEA, MEL, and MTN) can be purposely synthesized by adding SDAs of choice rather than relying on solvent decomposition. The Si atoms in zeolite Beta synthesized in a urea/choline chloride mixture exhibit exceptionally high local ordering as shown in a 29Si MAS NMR spectrum. The synthesis of ZSM-11 using eutectic solvents or ionic liquid has not been reported. The major challenge in ZSM-11 synthesis is the intergrown structure formed with ZSM-5 due to the high similarity in their topologies. The present work shows that preparation of pure ZSM-11 can be achieved in urea/choline chloride DES using either DPHMII or DECDMPI as SDA. Using a urea/choline chloride mixture rather than alcohol-based traditional nonaqueous solvents is the key for the success of preparing phase-pure ZSM-11 free of any MFI intergrowths. This is because some alcohols can serve as SDA for MFI. The use of urea/choline chloride based DES eliminates the potential templateing effect of solvent for MFI formation. For MTN zeolite, morphology may be controlled in urea/choline chloride by choosing different SDAs. The disadvantage of this system is the long reaction times.