Highly ordered supermicroporous aluminosilicates with cubic Pm3n symmetry fabricated in weakly acidic solution

Abstract

Highly ordered supermicroporous aluminosilicates with cubic Pm3n symmetry were prepared for the first time in weakly acidic solutions of succinic acid and malonic acid using dodecyltriethylammonium bromide as a template. The polycarboxylic acids acted as auxiliaries for fabricating the cubic Pm3n structure as well as weak acids. Thermally stable aluminosilicates with a high utilization ratio of Al could be obtained in the presence of succinic acid by either facilely adding aluminum source into the initial synthesis gel or by grinding the as-made silica-surfactant composite with aluminum nitrate. In contrast, thermally stable aluminosilicates could only be prepared via a post-synthesis approach in the presence of malonic acid, probably because of the powerful coordination tendency between malonic acid and Al cations. The thermal stability of the aluminosilicates was enhanced because of the incorporation of Al into the framework or grafting of Al onto the pore walls. Aluminosilicates prepared via the post-synthesis approach preserved the cubic Pm3n structure better than the directly-synthesized ones. In spite of the kind of polycarboxylic acids or the preparation methods, Al was predominantly tetrahedrally coordinated. The aluminosilicates showed a high specific area and pore volume, especially for the post-synthesized ones. The pore size was in the supermicroporous range evidenced by N₂ physisorption, though that of the aluminosilicates prepared via the post-synthesis approach was larger. TEM images verified the Pm3n symmetry of the materials herein. The cubic Pm3n aluminosilicates prepared in our research exhibited equal reactivity but a much pronounced deactivation resistance property in the acetalization of cyclohexanone with pentaerythritol.