Mesopore-selective incorporation of strong Bronsted acid catalytic sites via aluminium grafting on hierarchically porous siliceous MFI zeolite

Abstract

Post-synthetic Al grafting onto the surface silanols in mesoporous MFI zeolite has been investigated in an attempt to obtain a model catalytic material that possesses strong Brunsted acid sites at mesopore surfaces of the zeolite, but not inside the microporous framework. To this end, a siliceous MFI zeolite with a mesopore/micropore hierarchy was synthesized using a meso-micro dual structure-directing diammonium surfactant. The hierarchically porous zeolite was treated with anhydrous AlCl3 for the formation of Si-O-Al bonding with silanols on the mesopore surfaces. According to solid-state P-31 NMR spectroscopy of the surface-adsorbed phosphine oxides and catalytic activity for decalin cracking, the Al-grafting treatment performed in the conventional manner resulted in the formation of weak Brunsted acid sites, similar to Al grafting on SBA-15 mesoporous silica. To obtain strong Brunsted acid sites, we have developed a method of heating the AlCl3-grafted zeolite in a controlled-humidity chamber before calcination. The resultant zeolite was catalytically active for cracking of hydrocarbons requiring strong acid sites, but not for methanol-to-hydrocarbon conversion. The results support that the moisture treatment caused a local reconstruction of the initially grafted Al-O-Si framework portion to a strong Brunsted acid site. In addition, our model catalytic zeolite material unveiled the catalytic activity of Brunsted acid sites at the mesopore surfaces in hierarchically porous zeolite in n-octane cracking. Furthermore, we confirmed that this method was effective for other mesoporous MFI zeolites obtained through a post-synthetic desilication route.