Crystal Structures and in-Situ Formation Study of Mayenite Electrides

Mayenite inorganic electrides are antizeolite nanoporous materials with variable electron concentration [Ca₁₂Al₁₄O₃₂]²⁺□_5-δO_1-δ^2-e_2δ^- (0 < δ ≤ 1), where □ stands for empty sites. The oxymayenite crystal structure contains positively charged cages where loosely bounded oxide anions are located. These oxygens can be removed to yield electron-loaded materials in which the electrons behave like anions (electrides). Here, a new preparation method, which allows synthesizing powder mayenite electrides easily, is reported. Accurate structural data for the white (δ = 0) and green electride (δ ∼ 0.5) are reported from joint Rietveld refinements of neutron and synchrotron X-ray powder diffraction data and also from single-crystal diffraction. The electride formation at high temperature under vacuum has been followed in-situ by neutron powder diffraction. The evolution of mayenite crystal structure, including the changes in the key occupation factor of the intracage oxide anions, is reported. Furthermore, the stability of mayenite framework in very low oxygen partial pressure conditions is also studied. It has been found that C12A7 decomposes, at 1373 K in reducing conditions, to give Ca₅Al₆O₁₄ (C5A3) and Ca₃Al₂O₆ (C3A). The kinetics of this transformation has also been studied. The fit of the transformed fraction to the classic Avrami−Erofe'ev equation gave an “Avrami exponent”, n = 2, which indicates that nucleation is fast and the two-dimensional linear growth of the new phases is likely to be the limiting factor.