Observation of Water-Induced Synergistic Acidic Site from NMR-Invisible Al in Zeolite via Solid-State NMR Spectroscopy

Zeolites are highly sensitive to water, which significantly affects their acidity─a key factor in catalytic reactions. This study investigates the dynamic interactions between water and often overlooked active sites, specifically the "NMR-invisible" aluminum species (tricoordinated framework Al─FAL and cationic extra-framework Al─EFAL) in ultrastable Y (USY) zeolite under ambient conditions. Using solid-state NMR spectroscopy combined with theoretical calculations, we demonstrate that water readily undergoes dissociative adsorption on these "NMR-invisible" Al sites. This process transforms both FAL and EFAL into "NMR-visible" Al species. The formation of new Brønsted acid sites on tetra-, penta-, and hexa-coordinated FAL results in an increase of over 60% in the BAS concentration in the USY zeolite. The hydrolysis of EFAL cations leads to the formation of Brønsted/Lewis acid synergistic sites, significantly improving the catalytic activity of USY zeolite. This enhancement is evident in the improved conversion of diethyl ether to ethene in the presence of moisture.