Surface reducibility, reactivity, and stability induced by noble metal modifications on the ? -Fe2O3maghemite (001) surfaces

In these last years large research efforts have been devoted to the synthesis and investigation of reducible metal oxide surfaces modified with metal atoms and nanoparticles for improving their performance in a number of advanced applications. Among reducible metal oxides, iron oxides have the advantage to be made up from two of the most common elements on Earth. In this paper we analyze the structural, electronic, and magnetic consequences of the insertion of isolated noble metal atoms (Cu, Ag, Au) on the ?-Fe2O3 (001) surface. We have considered many different configurations for the single atoms: adsorbed, substitutional to iron atoms, or to oxygen atoms, and, using first principles calculations, we have studied how the presence of the noble metal atoms on the surface influences the surface stability, its reducibility, and, therefore, its catalytic activity, and how these properties depend on the kind of noble metal atom and its position. Our results show that noble metal atoms adsorbed on the surface facilitate the adsorption of CO molecules, and, among them, Cu atoms are those that bind best to the surface also providing the strongest adsorption energy for the CO molecule. At ambient temperature and pressure the noble metal atoms prefer to substitute the iron atoms than to just adsorb on the surface, but for Ag atoms the adsorption and substitutional energies are very close. The surfaces with Ag in place of Fe are the most reducible and reactive for exchange of oxygen atoms. Finally, Au is the best noble metal for oxygen substitution. Our results provide useful insights for the researchers designing and synthesizing new noble metal - iron oxides nanostructures for applications in biology, medicine, catalysis, and chemical analysis.