Synthesis of Microporous Aluminosilicate by Direct Thermal Activation of Phenyl-Substituted Single-Source...

The construction of aluminosilicates from versatile molecular precursors (MPs) represents a promising alternative strategy to conventional processes based on monomeric molecular or polymeric Al and Si sources. However, the use of MPs often suffers from drawbacks such as the decomposition of the core structures in the presence of solvents, acids, or bases. In this work, we demonstrate a simple thermal synthesis of porous aluminosilicates from single-source spiro-7-type MPs that consist of a tetrahedral Al atom and six Si atoms functionalized with 12 phenyl (Ph) groups, (C⁺)[Al{Ph₂Si(OSiPh₂O)₂}₂]^- (C; C⁺ = pyridinium cation (PyH⁺), Na⁺, K⁺, Rb⁺, or Cs⁺), without using a solvent or activator. Microporous aluminosilicates synthesized via the thermal treatment of C under a 79% N₂ + 21% O₂ atmosphere exhibited extremely low carbon contents (0.10-1.28%), together with Si/Al ratios of 3.9-6.7 ± 0.2 and surface areas of 103.1-246.3 m²/g. The solid-state ²⁷Al and ²⁹Si MAS NMR spectra suggest that the obtained aluminosilicates with alkali cations retain a tetrahedral Al site derived from the spiro-7-type core structure. After a proton-exchange reaction, the aluminosilicates showed almost 1.5 times higher reactivity in the catalytic ring-opening of styrene oxide than the aluminosilicate before proton exchange due to the catalytically active OH site being predominantly bridged by tetrahedral Al and Si atoms. These results suggest that the present MP strategy is a promising method for the introduction of key structures into active inorganic materials.