Modulation of Al Distribution in High-Silica ZSM-5 Zeolites for Enhancing Catalytic Performance

The spatial distribution of framework Al (Al_F) has been one of the important factors that affect the catalytic properties of zeolites in diverse chemical reactions; however, the synthesis of high-silica zeolites with special Al_F distribution remains a challenge. In this study, we successfully synthesized high-silica ZSM-5 zeolites with a unique Al_F distribution by employing pentaerythritol (PET) as an additive in the presence of a few tetrapropylammonium hydroxide (TPAOH). The results demonstrated that the introduction of PET led to a higher proportion of Al atoms located at the sinusoidal and/or straight channels. It was observed that the addition of PET prevented the interaction between TPA⁺ and tetrahedral [AlO₄]^- during the crystallization process, resulting in enhanced availability of TPA species in the form of ion-paired TPA⁺. This effect leads to Al_F atoms dominantly distributed away from the intersection and located in narrow channels, where acidic sites more effectively inhibit hydrogen transfer and coke formation. In the reaction of dimethyl ether (DME) to olefins, the catalyst with a unique Al distribution exhibited a significant prolonged catalytic lifetime, surpassing traditional TPA-ZSM-5 by more than 2-fold and maintaining DME conversion above 90% for a maximum of 148 h. The results of multiple pulse experiments also showed that these PET-assisted ZSM-5 zeolites significantly enhanced the selectivity of propene and butene. This approach provides an effective strategy to regulate Al_F distribution in high-silica ZSM-5 catalysts with the assistance of neutral alcohol. It holds great potential for application in the synthesis of other high-silica zeolites, thereby enriching the diversity of zeolite catalysis.