Understanding Structure and Stability of Monoclinic Zirconia Surfaces from First-Principles Calculations

Under the water-rich pre-treatment and/or reaction conditions, structure and chemistry of the monoclinic zirconia surfaces are strongly influenced by oxygen vacancies and incorporated water. Here, we report a combined first-principles and atomistic thermodynamics study on the structure and stability of selected surfaces of the monoclinic zirconia. Our results indicate that among the studied surfaces, the most stable (111) surface is the least vulnerable towards oxygen vacancies in contrast to the less stable (011) and (101) surfaces, where formation of oxygen vacancies is energetically more favorable. Furthermore, we present a vigorous, systematic screening of water incorporation onto the studied surfaces. We observe that the greatest stabilization of the surfaces is achieved when a part of the adsorbed water molecules is dissociated. Nevertheless, the importance of water dissociation for achieving the greatest stabilization is high for the less stable (011) and (101) surfaces, while completely hydrated (111) surface is stabilized equally regardless of the water dissociation state. Analysis of the constructed phase diagrams reveals that the (111) surface remains preferably clean and the (011) and (101) surfaces have dissociated water at low coverage under the reactive conditions of T = 600–900 K and p(H2O) < 1 bar. Upon temperature decrease and/or pressure increase, all studied surfaces gradually uptake water until fully hydrated. All in all, our findings complement and broaden the existing picture of the structure and stability of the monoclinic zirconia surfaces under the pre-treatment and/or reaction conditions, enabling rationalization of the potential roles of zirconia as a heterogeneous support and a catalyst component.