First-principles analysis of vacancy-assisted reaction on metal-doped t-$ZrO_{2}$ surfaces

Vacancy-assisted reaction on tetragonal (t-) $ZrO_{2}$ surface is important for its potential in combustion synthesis, barrier coating and as solid electrolyte in solid-oxide fuel cells. Doping or alloying the surface could significantly enhance the surface reactivity and transport by altering the electronic structure of the surface. We performed first-principles analysis on the metal doped t-$ZrO_{2}$ surfaces to assess the role of metal doping on the vacancy-assisted reaction at t-$ZrO_{2}$. Vacancy formation energy was calculated for 14 different doping metals. Most impurity metals from 4th and 5th row of periodic table promote formation of vacancies on the surface. Electronic structure of the defect state with respect to filled states and vacancy diffusion barriers will be discussed. Furthermore, the analysis is extended to surface reactivity for oxygen adsorption during combustion reaction of Zr particles and barrier properties against water mediated corrosion processes. For both cases, an analysis of reaction rates under different temperatures and pressures for different t-$ZrO_{2}$ surfaces will be discussed.