Effect of R-site element on crystalline phase and thermal stability of Fe substituted Mn mullite-type oxides: R2(Mn1?xFex)4O10?δ (R = Y, Sm or Bi; x = 0, 0.5, 1)

摘要

Combining experimental and theoretical studies, we investigate the role of R-site (R = Y, Sm, Bi) element on the phase formation and thermal stability of R _(2) (Mn _(1? x ) Fe _( x ) ) _(4) O _(10? δ ) ( x = 0, 0.5, 1) mullite-type oxides. Our results show a distinct R-site dependent phase behavior for mullite-type oxides as Fe is substituted for Mn: 100% mullite-type phase was formed in (Y, Sm, Bi) _(2) Mn _(4) O _(10) ; 55% and 18% of (Y, Sm) _(2) Mn _(2) Fe _(2) O _(10? δ ) was found when R = Y and Sm, respectively, for equal Fe and Mn molar concentrations in the reactants, whereas Bi formed 54% O10- and 42% O9-mixed mullite-type phases. Furthermore, when the reactants contain 100% Fe, no mullite-type phase was formed for R = Y and Sm, but a sub-group transition to Bi _(2) Fe _(4) O _(9) O9-phase was found for R = Bi. Thermogravimetric analysis and density functional theory (DFT) calculation results show a decreasing thermal stability in O10-type structure with increasing Fe incorporation; for example, the decomposition temperature is 1142 K for Bi _(2) Mn _(2) Fe _(2) O _(10? δ ) vs. 1217 K for Bi _(2) Mn _(4) O _(10) . On the other hand, Bi _(2) Fe _(4) O _(9) O9-type structure is found to be thermally stable up to 1227 K. These findings are explained by electronic structure calculations: (1) as Fe concentration increases, Jahn–Teller distortion results in mid band-gap empty states from unstable Fe ~(4+) occupied octahedra, which is responsible for the decrease in O10 structure stability; (2) the directional sp orbital hybridization unique to Bi effectively stabilizes the mullite-type structure as Fe replaces Mn.