Hydrogen bonding to oxygen in siloxane bonds drives liquid phase adsorption of primary alcohols in high-silica zeolites

Abstract

Upon liquid phase adsorption of C₁–C₅ primary alcohols on high silica MFI zeolites (Si/Al = 11.5–140), the concentration of adsorbed molecules largely exceeds the concentration of traditional adsorption sites: Brønsted acid and defect sites. Combining quantitative in situ¹H MAS NMR, qualitative multinuclear NMR and IR spectroscopy, hydrogen bonding of the alcohol function to oxygen atoms of the zeolite siloxane bridges (Si–O–Si) was shown to drive the additional adsorption. This mechanism co-exists with chemi- and physi-sorption on Brønsted acid and defect sites and does not exclude cooperative effects from dispersive interactions.