Interaction of Hydrogen with Cu-Modified Cerium Oxide Surfaces

We investigate the interaction between molecular hydrogen and ultrathin epitaxial CeO2 films modified with a 2% concentration of Cu atoms using X-ray photoemission spectroscopy (XPS) during thermal reduction cycles in H2. The XPS measurements are combined with density functional theory calculations to obtain further insight into the observed modifications of the film surface. Our results show that the presence of Cu atoms decreases the barrier for H2 dissociation in comparison to that on pure ceria surfaces, leading to the formation of surface OH groups after exposure to H2. Moreover, surface oxygen vacancies are generated already at mild temperatures (470 K), most likely via water formation and desorption. The presence of surface oxygen vacancies and hydroxyls contributes to the observed large increase in surface Ce3+ concentration with increasing reduction temperature. In spite of these atomic scale modifications, the surface morphology observed by scanning tunneling microscopy remains substantially unchanged on the length scale of tens of nm.

Automated summary

We investigated the interaction between molecular hydrogen and ultrathin epitaxial CeO2 films modified with a 2% concentration of Cu atoms using X-ray photoemission spectroscopy (XPS) and density functional theory calculations. The presence of Cu atoms was found to decrease the barrier for H2 dissociation, leading to the formation of surface OH groups. Additionally, surface oxygen vacancies and hydroxyls were generated at relatively low temperatures, contributing to the increase in surface Ce3+ concentration.