Overgrowth of lamellar silicalite-1 on MFI and BEA zeolites and its consequences on non-oxidative methane aromatization reaction

The combination of two compositionally and/or structurally different zeolites into one single zeolite composite particle is a potential approach to integrate advantages of different zeolite structures for desirable properties and applications. In the present study, we report the overgrowth of lamellar mesoporous silicalite-1 on the commercial microporous MFI and BEA zeolites, respectively, to render hierarchical meso-/microporous lamellar silicalite-1/MFI (L-Si/MFI) and lamellar silicalite-1/BEA (L-Si/BEA) zeolite composites via hydrothermal crystallization of lamellar silicalite-1 with the assistance of a diquaternary ammonium template. Epitaxial growth of lamellar silicalite-1 on commercial bulk MFI was observed, resulting in the L-Si/MFI zeolite composite as porcupine sensory message ball with nerve-stimulating silicalite-1 bumps extended from the MFI particle. In the L-Si/BEA zeolite composite, the lamellar silicalite-1 was laid over the surface of or partially interdigitated into the commercial bulk BEA particle, forming a BEA nanosponge structure connected to lamellar silicalite-1 nanosheets. The resultant interconnected micro- and mesoporosity in the L-Si/MFI and L-Si/BEA composite zeolites allowed facile mass transport of bulky molecules. The acid sites sitting on the external surface of commercial MFI and BEA zeolites were partially passivated by the lamellar silicalite-1. The consequences of improved mass transport and passivation of external acid sites on the catalytic performance of these zeolite composites were tested in 2 wt% molybdenum (Mo) loaded L-Si/MFI and L-Si/BEA for direct non-oxidative methane aromatization reaction, which showed higher methane conversion and hydrocarbon product formation as well as higher selectivity to naphthalene and coke in comparison with 2 wt% Mo-loaded commercial MFI and BEA catalysts.