Theoretical Investigation of Supported Utra-Thin Bilayer, Double Bilayer and Trilayer Metal-Oxides: Structure, Stabilty and Catalytic Activity

In the last decade, a number of experiments have shown that ultra-thin layers of transition metal oxides (TMOs) can be stabilized when interfaced with precious metal supports such as Au(111) and Pt(111) or Ir(100). Moreover, gold supported Co/Ni/Mn-based catalysts have been experimentally proven to exhibit higher oxygen evolution reaction (OER) activities than other metal supported oxide catalysts. Recetly, we have explained the synergistic effect of contact with gold support for Ce-doped NiOx catalyst (10.1038/nenergy.2016.53). Furtermore, we have linked experimentally and theoretically a high H2O reactivity of ultra-thin cobalt oxide nanoislands supported on Au(111) to high edge reactivity of the bilayer systems. The calculated trends in the thermodynamic stability of ultrathin supported oxide films reveals that single metal adsortion energy is a reasonable descriptor for the stability of the overlayers, but larger errors appear for films with large lattice mismatch (10.1021/acs.jpcc.6b01404). I will also present results for the the comparative analysis of cobalt oxide nanoisland stability on three related noble metal surfaces: Au(111), Pt(111) and Ag(111). Fundamental understanding in terms of surface polarity, lattice mismatch and charge trasfer properties will be discussed as well as applications to other catalystics process that OER such as hydrogen evolution reaction (HER) and CO2 reduction reaction (CO2RR).