Acid−Base Characterization of Aluminum Oxide Surfaces with XPS

The localized acid−base properties of different, aluminum oxide thin layer surfaces have been evaluated with X-ray photoelectron spectroscopy (XPS). Five types of oxide layers were studied, which were produced by oxidizing aluminum in a vacuum, with an alkaline and acidic pretreatment, and in boiling water. The photoelectron core level binding energies, as measured with XPS, are evaluated for this purpose, while taking into consideration the initial and final state effects. For the structurally comparable oxides, the shifts in the O 1s binding energies are determined by their initial state chemistry. The values of the O 1s binding energy can be directly related to the surface-averaged charge on the O anions. For the Al cations, a correlation between the photoelectron core level binding energy shift and changes in the initial state chemistry was observed, but the Al 2p binding energy shifts were found to be partially due to changes in extra-atomic relaxation. The measured Al 2p binding energies and the binding energies of the resolved OH and O components in the O 1s peak showed that the studied aluminum oxides have OH sites with the same Brönsted/Lewis acid−base properties, O sites with the same Lewis base properties, and Al sites with very similar Lewis acid properties. The pseudoboehmite oxide, obtained by boiling aluminum in water, exhibits more basic O, OH, and Al sites. This oxide deviates structurally from the other oxides studied, resulting in a lower extra-atomic relaxation and Madelung potential contribution to the binding energies.