Phase stability and structure of spinel-based transition aluminas

Using first-principles total energy calculations, we have investigated the structure and phase stability of spinel-based transition aluminas(γ, δ, η), both in the presence and absence of hydrogen. The spinel-based structures (formed from dehydration of aluminum hydroxides) necessarily must have vacant cation positions to preserve the Al₂O₃ stoichiometry, and may have residual hydrogen cations in the structure as well. In the absence of hydrogen, we find the following: (i) Vacancies in octahedral sites are energetically preferred (or, Al cations prefer tetrahedral positions). (ii) There is a strong Al-vacancy ordering tendency, with widely separated vacancies being lower in energy than near-neighboring vacancies. Upon incorporation of hydrogen into the structure: (iii) The strong cation-vacancy ordering tendency vanishes, and “clusters” of near-neighbor vacancies are slightly energetically preferred. (iv) The hydrogen spinel (HAl₅O₈) proposed in the literature as a structural candidate for γ-alumina, is thermodynamically unstable with respect to decomposition into the anhydrous defect spinel plus boehmite (γAlOOH). (v) The temperature range for transforming boehmite into γ − Al₂O₃ is calculated from first-principles energetics plus measured thermochemical data of H₂O, and is in excellent agreement with the observed transformation temperatures. Finally, we comment on the possible implications of this work on the porous microstructure of the transition aluminas.