Effect of Al content on number and location of hydroxyl acid species in zeolites: a DRIFTS quantitative protocol without the need for molar extinction coefficients?

RSC Advances Pub Date: 2017-11-14 DOI: 10.1039/C7RA10699H

Abstract

In this work, we have systematically investigated the effect of the Al content on the number and location of bridging hydroxyls (Br?nsted acid sites) and terminal hydroxyls (terminal silanol sites) in ZSM-5 zeolites with varying silica-alumina ratio (SAR = SiO2/Al2O3) using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) without molar extinction coefficients. Two base probe molecules with different kinetic diameters, pyridine (5.7 ?) and collidine (7.4 ?), were used. The total content of Br?nsted acid sites is obtained by elemental analysis of the proton form and sodium exchanged form of ZSM-5. To quantify the number of internal and external Br?nsted acid sites the change in area of the Br?nsted acid site peak in the O–H stretching region is then used; thus, the need for molar extinction coefficients to quantify Br?nsted acid sites is thereby eliminated. The results reported here show that for ZSM-5 the number of external Br?nsted sites, in absolute terms, increases with increasing total Al content, as evidenced by collidine adsorption. The number of terminal silanol acid sites was found to be proportional to the external surface area probed by argon sorption experiments. In summary, this work shows that the use of DRIFTS in conjunction with elemental analysis is a valid alternative to qualitatively and quantitatively probe the number and location of hydroxyl acid sites without the use of molar extinction coefficients and gives a comprehensive picture of the effect of Al content on number and location of hydroxyl acid species in ZSM-5 zeolites with varying SAR. The work contributes to advancing the range of characterisation protocols for solid acid catalysts.

Graphical abstract: Effect of Al content on number and location of hydroxyl acid species in zeolites: a DRIFTS quantitative protocol without the need for molar extinction coefficients
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