Tailoring manganese oxide with atomic precision to increase surface site availability for oxygen reduction catalysis

Controlling the structure of catalysts at the atomic level provides an opportunity to establish detailed understanding of the catalytic form-to-function and realize new, non-equilibrium catalytic structures. Here, advanced thin-film deposition is used to control the atomic structure of La(2/3)Sr(1/3)MnO(3), a well-known catalyst for the oxygen reduction reaction. The surface and sub-surface is customized, whereas the overall composition and d-electron configuration of the oxide is kept constant. Although the addition of SrMnO(3) benefits the oxygen reduction reaction via electronic structure and conductivity improvements, SrMnO(3) can react with ambient air to reduce the surface site availability. Placing SrMnO(3) in the sub-surface underneath a LaMnO(3) overlayer allows the catalyst to maintain the surface site availability while benefiting from improved electronic effects. The results show the promise of advanced thin-film deposition for realizing atomically precise catalysts, in which the surface and sub-surface structure and stoichiometry are tailored for functionality, over controlling only bulk compositions.