Probing Brønsted Acidity of Protonic Zeolites with Variable-Temperature Infrared Spectroscopy

Abstract

Most industrial applications of zeolites as solid-acid catalysts rely on their high Brønsted acidity, which affects both catalytic activity and selectivity, and hence the convenience to find an accurate experimental technique for measuring the acid strength. The enthalpy change, ΔH0, involved in the hydrogen bonding interaction between a weak base (such as carbon monoxide) and the Brønsted acid [Si(OH)Al] hydroxyl groups should correlate directly with the zeolite acid strength. However, on account of simplicity, the bathochromic shift of the O–H stretching frequency, Δv(OH), is usually measured by IR spectroscopy at a (fixed) low temperature in-stead of ΔH0 and correlated with the acid strength for ranking the zeolite acidity. Herein, the use of variable-temperature IR spectroscopy to determine simultaneously ΔH0 and Δv(OH) is demonstrated, followed by a review of recent experimental results showing that the practice of ranking the acid strength by the corresponding O–H frequency shift probed by a weak base could be misleading; and that can be so much the case of zeolites showing a wide range of structure types.