Surface acidity study of Mn+-montmorillonite clay catalysts by FT-IR spectroscopy: Correlation with esterification activity

A simple method for evaluating the surface acidity of different cation-exchanged montmorillonite (mont) clay catalysts, Mn+-mont (Mn+=Al3+, Fe3+, Cr3+, Zn2+, Ni2+, Cu2+, and H+), involving treatment with pyridine is described. After treating with pyridine, the samples were heated at 120 °C and the FT-IR spectra were directly recorded in the region 1650 and 1350 cm−1. The data obtained show the presence of both Lewis and Brønsted acid sites. The activities of the catalysts to bring about Brønsted acid catalysed esterification of succinic acid with iso-butanol to yield di-(iso-butyl) succinate have been studied. The Brønsted acidity data obtained for Mn+-mont correlated well with activity in the esterification reaction. The activities of the catalysts were found to decrease in the order of exchange ions Al3+ > Fe3+ > Cr3+ > Zn2+ > Ni2+ > Cu2+ > Na+-mont. They also correlated well with the charge to radius ratio of the cations. The catalysts exchanged with trivalent cations showed stronger absorption bands attributed to Brønsted acidity (1540 cm−1) whereas those exchanged with divalent cations showed an increased Lewis acidity (1450 cm−1) and reduced Brønsted acidity along with charge to radius ratio. Zn2+-, Cu2+- and Ni2+-exchanged clays showed an additional peak around 1605 cm−1 which is attributed to the pyridine adsorption on surface sites through its π electrons. The method suggested here to evaluate the acidity is suitable for active sites which are thermally unstable such as water molecules in the hydration shell of a cation in exchanged clay