Low-Temperature Fourier-Transform Infrared Investigation of the Interaction of CO with Nanosized ZSM5 and Silicalite

Nanosized ZSM5 zeolites with microcrystal dimensions in the 20-120 nm range have been characterized by means of IR spectroscopy and HRTEM microscopy. The vibrational spectrum of the OH groups on the external and internal surfaces of H-ZSM5 and Na-ZSM5 samples of different crystallite dimensions has been investigated. For the sake of comparison the spectra of silicalite samples containing different concentrations of sodium and aluminium are also shown. For this purpose high-purity silicalite samples were prepared following a novel synthesis route. Carbon monoxide (a very weak Lewis base) was used to probe the acidity present on the external and internal surfaces of the zeolites through formation of 1 : 1 addducts with silanols (both internal and external), Bronsted-acid groups (both framework and extraframework), Na+ ions, and Lewis Al3+ centres (in extraframework and framework positions). The IR-active CO stretching modes of the complexes are shifted to higher wavenumber with respect to the free molecule; the positive shift can be used to estimate the acid strength. CO that was physically adsorbed in the zeolite channels has also been investigated.