AP-XPS Study of Ethanol Adsorption on Rutile TiO₂(110)

The photoactivity of rutile TiO₂(110) renders its surfaces of particular interest for the study of surface reactions. In particular, rutile TiO₂(110) surfaces are active for hydrogen production, both via the water splitting process and via ethanol degradation under ultraviolet illumination. The selective photocatalytic dehydrogenation of rutile TiO₂(110) is not fully understood yet, and an important question in this context is how ethanol adsorbs onto the rutile TiO₂(110) surface under ambient conditions. Here, we present the first in situ experimental study on the absorption of ethanol on rutile TiO₂(110) at room temperature and near-ambient conditions. The surface sensitivity of synchrotron-based ambient pressure X-ray photoelectron spectroscopy allows for an in-depth analysis of the surface species (molecular ethanol and ethoxies) and their coverage as well as an estimation of the energy difference between the two species. Through modeling of the O 1s core level and comparison to experimental results we show that both molecular and dissociative adsorption of ethanol occurs. The difference in adsorption energy range calculated from modeling of the O 1s core level was 0.018-0.033 eV, with dissociative adsorption the most energetically favorable. The difference in adsorption energy is almost an order of magnitude lower than previous estimations from theoretical calculations. In addition, we show that at room temperature a multilayer is formed with increasing pressure of ethanol.