Identification and Quantification of Al Pairs and Their Impact on Dealumination in Zeolites

Understanding the precise quantity and spatial distribution of paired aluminum (Al) sites in zeolite catalysts is crucial, as they significantly impact the catalytic performance via synergistic effects and long-term stability. In this study, a novel strategy by employing divalent cation titration with varying cation sizes, in combination with advanced quantitative ¹H NMR and ¹H-¹H homonuclear correlation techniques, has been developed to accurately identify and classify three distinct types of Al pairs. These include two types of Al pairs aligned along six-membered rings (6-MRs) and 10-membered rings (10-MRs), the latter of which are essentially composed of Al atoms located in different 6-MR or 5-MR. The third type comprises two Al atoms located in different channels. The second and third types had been challenging to probe in the past, yet they may be critical for catalysis, particularly the second type demonstrating proximity close enough to accommodate Ba²⁺ (with a radius of 1.49 Å). Our strategy for quantifying each type of Al pair marks a significant advancement in the understanding of the zeolite framework. Furthermore, controlled hydrothermal treatments using stepwise steaming reveal that a higher concentration of Al pairs accelerates dealumination, primarily for dynamic reasons of water molecules but not intrinsic structural instability induced by Al pairs. To address this, we propose a "bi-Al" vs "mono-Al" hydrolysis model, offering fresh insights into the pivotal role of Al pairs on zeolite stability. This work opens new avenues for optimizing zeolite-based catalysts for enhanced performance and longevity.