Deleterious effects of non-framework Al species on the catalytic performance of ZSM-5 crystals synthesized at low temperature†
ZSM-5 is one of the most widely studied and commercially relevant zeolites. It is also one of the few zeolites that can be synthesized in an all-silica form (silicalite-1), and thus serves as a prototype for mechanistic studies of zeolite crystallization. The MFI framework of ZSM-5 is amenable to a broad range of synthesis conditions, which has led to numerous discoveries of materials with unique physicochemical properties. The exceptional performance of ZSM-5 among zeolite catalysts, coupled with its facile synthesis, has given rise to its widespread use in industrial applications. In this study we highlight the challenges associated with synthesizing ZSM-5 at low temperature (ca. 100 °C), which is often necessary to generate small crystals (<200 nm) with an appreciable quantity of acid sites (i.e. Si/Al < 25). We focus on the incorporation of non-framework Al, which includes extra-framework (octahedral) Al and penta-coordinated Al, as well as Al zoning – a common phenomenon where the density of Al sites within the framework is more prevalent at the outer rim and exterior surfaces of ZSM-5 crystals. We show that synthesis at low temperature, and most notably in growth mixtures containing high aluminum concentration, results in the incomplete incorporation of Al into the ZSM-5 framework that can be partially removed through post-synthesis mild acid treatment. We also show that higher synthesis temperature (170 °C) facilitates the incorporation of framework Al; however, in all cases the catalysts prepared in this study exhibit relatively low activity owing in part to the presence of Al defects. The library of ZSM-5 catalysts prepared herein are characterized using methanol to hydrocarbons as a benchmark reaction to assess the performance of various as-made and acid treated samples. Our findings suggest that ZSM-5 may be more difficult to synthesize than is commonly perceived, most notably when examining the various types of defects in crystalline products over a wide range of synthesis conditions.