In situ FTIR spectra of pyridine adsorbed on SiO 2–Al 2O 3, TiO 2, ZrO 2 and CeO 2: general considerations for the identification of acid sites on surfaces of finely divided metal oxides

Abstract

Exposure of strong Lewis (coordinatively unsaturated metal atoms) and Bronsted (proton donor OH-groups) acid sites on solid surfaces is a prime demand for potential adsorptive and catalytic applications. In situ FTIR spectroscopy of small adsorbed base molecules, often NH 3, pyridine, CH 3CN, NO or CO molecules, has been well established as a powerful surface analytical technique for characterization of nature, strength and concentration of acid sites. Pyridine (Py) has been preferred as an IR probe molecule of finely divided metal oxide surfaces at room (RT) and higher temperature regimes, since it is (i) more selective and stable than NH 3; (ii) much more strongly adsorbed than CO and CH 3CN; and (iii) relatively more sensitive to the strength of Lewis acid sites than NO. In the present work, in situ IR spectra of Py adsorbed at ≥RT on characterized alumina, silica, silica–alumina, titania, zirconia and ceria were measured, and compared with RT-spectra of liquid and gas phase Py obtained under identical spectroscopic conditions, in order to characterize spectral consequences of mutual Py–Py interactions in the adsorbed phase. It has been concluded that the availability of Lewis acid sites can be unequivocally monitored by formation of coordinated Py molecules giving rise to IR-absorption(s) due to the ν 8a mode of νCCN vibrations at 1630–1600 cm −1, where the higher the frequency assumed, the stronger the acidity of the site. Formation of pyridinium surface species (PyH +) is identifiable by (i) an ν 8a-absorption at ≥1630 cm −1; (ii) an ν 19b-absorption at 1550–1530 cm −1; as well as (iii) νN +H and δN +H absorptions occurring, respectively, near 2450 and 1580 cm −1, and, thus, the availability of Bronsted acid sites. Moreover, products and IR-characteristics of Py surface reactions at >RT have been identified, and used to imply nature of surface base sites (OH −and O 2−) involved in formation of acid–base site pairs.