Tailoring Hierarchical Zeolites with Designed Cationic Surfactants and Their High Catalytic Performance.

Three hierarchical porous zeolites (H-*BEA, H-MTW, and H-*MRE) were successfully synthesized with the assistance of designed cationic surfactants under hydrothermal synthesis conditions. The as-synthesized zeolite samples can be easily regulated by changing the number of long hydrophobic n-alkyl chains. Also, we investigated the relationship between the length of the surfactant and the formation of the microporous structure of the zeolite. Furthermore, the alkylation of benzene with propene was performed as a probe reaction to evaluate the catalytic performance of the synthesized hierarchical zeolites. The resulting materials were characterized by using a complementary combination of techniques, that is, X-ray powder diffraction, N adsorption-desorption isotherms, scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, Si and Al MAS NMR spectroscopies, thermogravimetric analysis, and computer simulation. These analysis results indicated that quaternary ammonium surfactants acted as organic structure-directing agents (OSDAs) in the formation of these hierarchical zeolite samples, whether the surfactant had long hydrophobic tail groups or not. The simulation results indicated that the organic molecules with no long hydrophobic chain could lead to the synthesis of zeolite through charge control, and the hydrophobic molecules with long hydrophobic chains could form zeolites through orbital control. These hierarchical zeolites showed improved catalytic activity towards the industrially relevant alkylation of benzene with propene compared with conventional zeolites with the same frameworks. More importantly, the success of using quaternary ammonium surfactants with no hydrophobic n-alkyl tail group in the synthesis of hierarchically structured mesoporous zeolites provides a new pathway for the synthesis of hierarchical porous materials by a soft-templating method.