Effect of Al content on the strength of terminal silanol species in ZSM-5 zeolite catalysts: a quantitative DRIFTS study without the use of molar extinction coefficients

Abstract

The strength of terminal hydroxyl Si-OH groups (silanols) in zeolites is important for many non-size-selective catalytic reactions occurring onto the external surface of the zeolite crystals and may often be responsible for catalyst deactivation, e.g., coke formation. A quantitative analysis of Si–OH strength and its link with the Al content, hence varying silica-to-alumina ratio (SAR = SiO₂/Al₂O₃), has not been established yet. Various hypotheses have been proposed in the literature; nonetheless, the role of Al content in determining silanol strength remains still unclear and the object of speculation. In this work, we have systematically investigated the effect of the Al content on the strength of terminal silanol sites in ZSM-5 zeolite catalysts with varying SAR using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) at variable temperatures without molar extinction coefficients. Two base probe molecules with different proton affinity values, pyridine and collidine, were used. To quantify the strength of terminal silanol sites the change of the terminal silanol peak in the OH stretching region, together with data on elemental analysis, was used. With this experimental protocol, unlike most IR studies, the use of molar extinction coefficients, often difficult to obtain, is not needed for quantification. The results reported here show for the first time that for ZSM-5 zeolite catalysts the fraction of occupied terminal silanol acid sites for both pyridine and collidine increases with increasing concentration of external Brønsted acid sites, hence establishing a clear link between the two types of acid sites. In summary, this work shows that the use of DRIFTS without molar extinction coefficients is able to quantitatively probe the strength of terminal silanol acid sites and establishes a link between the external Brønsted Al content and the strength of terminal silanol species in ZSM-5 zeolites with varying SAR at elevated temperatures.