Steam-Induced Aluminum Speciation and Catalytic Enhancement in ZSM-5 Zeolites

ZSM-5 zeolites with varying aluminum content were subjected to steam treatments of different severities by adjusting the temperature, duration, and water vapor pressure. The steamed samples were characterized using a range of analytical techniques. A quantitative assessment of the aluminum species—namely, tetrahedrally coordinated framework Al, dislodged framework Al, non-framework pentacoordinated Al, and non-framework hexacoordinated Al—was achieved through a combination of EDX analysis on Cs-exchanged materials and quantitative ²⁷Al MAS NMR spectroscopy, including spectral simulation. Contrary to previous reports, the catalytic activity per framework Al site in unsteamed ZSM-5 increases with aluminum content at low Si/Al ratios, aligning with recently proposed medium effects. Notably, at the point of maximum activity enhancement due to steaming, equivalent amounts (1:1) of framework and dislodged framework Al—both in tetrahedral coordination—are observed. The maximum enhancement factor per framework Al site, for a given material and reaction, remains independent of the specific steaming conditions (temperature, time, and pressure). However, the degree of activity enhancement varies with the type of reaction: it is more pronounced for n-hexane cracking (α-test) than for m-xylene isomerization. This suggests that both catalyst modification and reaction characteristics contribute to the observed steam-induced activity enhancement. A synergistic interaction between Brønsted and Lewis acid sites appears to underpin these effects. One plausible mechanism involves the strengthening of Brønsted acidity in the presence of adjacent Lewis acid sites. This enhancement is expected to be more significant for n-hexane cracking, which demands higher acid strength compared to m-xylene isomerization. In cases of n-hexane cracking, the increased acid strength and the formation of olefins via reactions on Lewis acid sites may act cooperatively. Importantly, the dislodged framework Al species—tetrahedrally coordinated in the hydrated catalyst at ambient temperature and functioning as Lewis acid sites in the dehydrated zeolite under reaction conditions—are directly responsible for the observed enhancement in acid activity. The transformation of framework Al into dislodged framework Al species is reversible, as demonstrated by hydrothermal treatment of the steamed samples at 150–200 °C. Nonetheless, reinsertion of Al into the framework is not fully quantitative: a portion of the dislodged framework Al is irreversibly converted into non-framework penta- and hexacoordinated species during the hydrothermal process. Among these, non-framework pentacoordinate Al species may serve as counterions to balance the lattice charges associated with framework Al.