An infrared spectroscopic investigation of thin alumina films: measurement of acid sites and surface reactivity

The surface chemical activity of an alumina films grown on Mo(100) by oxidation of aluminum evaporated onto the surface and oxidized using water is examined using Auger, X-ray photoelectron and reflection/absorption infrared spectroscopies. The formation of alumina is confirmed using Auger and X-ray photoelectron spectroscopy from the positions and intensities of the aluminum features and using reflection-absorption infrared spectroscopy from the longitudinal optical modes of the Al–O bonds measured at 935 cm⁻¹. The presence of surface hydroxyls is monitored by forming films using D₂O which are evidenced by a feature at 2700 cm⁻¹. Ammonia adsorption on a dehydroxylated surface yields a single peak at 1260 cm⁻¹ due to ammonia adsorbed at a surface Lewis site where the principle symmetry axis of ammonia is oriented perpendicularly to the surface plane. Ammonia also appears to adsorb at Lewis sites on a hydroxylated surface with a slightly different adsorption geometry from that on a dehydroxylated surface. Finally, the chemistry of trimethyl aluminum adsorbed on the planar hydroxylated alumina surface is compared with that found on high-surface-area γ-alumina where the spectra and the chemistry found in both régimes is exactly identical except that the low-frequency methyl bending modes (at 769 and 718 cm⁻¹) are not obscured on the thin film by the intense substrate whereas they are on the high-surface-area support.