Assessment, Control, and Impact of Brønsted Acid Site Heterogeneity in Zeolite HZSM-5

Acidic zeolites are solid aluminosilicate catalysts whose utility arises from Brønsted sites that predominately reside in their crystalline framework structure. Data described herein indicate that extra-framework aluminum (EFAl) moieties, often proposed as important species in overall catalyst activity via Brønsted–Lewis synergies, can themselves contribute protons that are also reactive Brønsted acid centers. While the MFI family of zeolites is a relatively simple channel-structure type, the quantitative spectroscopic detection of all protons shows that the distribution of reactive Brønsted acid site protons arising from framework and extra-framework moieties can be complex. Experiments show that postsynthetic treatments can be used to modify this distribution, in theory enabling routes to HZSM-5 catalysts with only one type of reactive Brønsted site. Quantitative spin-counting NMR experiments combined with chemical washing using ammonium hexafluorosilicate (AHFS) show that the number of framework bridging acid sites (BAS) in typical commercial MFI catalysts (Si/Al equal 15 and 40) is between 50 and 60% of that expected based on the total Al content. Acidic protons from EFAl constitute the major fraction of remaining Brønsted sites. Probe-molecule reactions demonstrate that catalysts with only framework BAS are significantly less reactive than those with both extra-framework and framework Brønsted acid sites. Various postsynthetic methods are compared to optimize the desired Brønsted acid site distribution in MFI catalysts, including both removal and re-introduction of acidic protons from EFAl sites.