title: Localization of oxygen interstitials in CeSrGa3O(7+δ) melilite.
abstract: The solubility of Ce in the La(1-x)Ce(x)SrGa3O(7+δ) and La(1.54-x)Ce(x)Sr0.46Ga3O(7.27+δ) melilites was investigated, along with the thermal redox stability in air of these melilites and the conductivity variation associated with oxidization of Ce(3+) into Ce(4+). Under CO reducing atmosphere, the La in LaSrGa3O7 may be completely substituted by Ce to form the La(1-x)Ce(x)SrGa3O(7+δ) solid solution, which is stable in air to ∼600 °C when x ≥ 0.6. On the other side, the La(1.54-x)Ce(x)Sr0.46Ga3O(7.27+δ) compositions displayed much lower Ce solubility (x ≤ 0.1), irrespective of the synthesis atmosphere. In the as-made La(1-x)CexSrGa3O(7+δ), the conductivity increased with the cerium content, due to the enhanced electronic conduction arising from the 4f electrons in Ce(3+) cations. At 600 °C, CeSrGa3O(7+δ) showed a conductivity of ∼10(-4) S/cm in air, nearly 4 orders of magnitude higher than that of LaSrGa3O7. The oxidation of Ce(3+) into Ce(4+) in CeSrGa3O(7+δ) slightly reduced the conductivity, and the oxygen excess did not result in apparent increase of oxide ion conduction in CeSrGa3O(7+δ). The Ce doping in air also reduced the interstitial oxide ion conductivity of La1.54Sr0.46Ga3O7.27. Neutron powder diffraction study on CeSrGa3O7.39 composition revealed that the extra oxygen is incorporated in the four-linked GaO4 polyhedral environment, leading to distorted GaO5 trigonal bipyramid. The stabilization and low mobility of interstitial oxygen atoms in CeSrGa3O(7+δ), in contrast with those in La(1+x)Sr(1-x)Ga3O(7+0.5x), may be correlated with the cationic size contraction from the oxidation of Ce(3+) to Ce(4+). These results provide a new comprehensive understanding of the accommodation and conduction mechanism of the oxygen interstitials in the melilite structure.
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University , Guangzhou 510275, P. R. China.
authors.forename: Jungu
authors.initials: J
authors.lastname: Xu
authors.forename: Xiaojun
authors.initials: X
authors.lastname: Kuang
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Véron
authors.forename: Mathieu
authors.initials: M
authors.lastname: Allix
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Suchomel
authors.forename: Florence
authors.initials: F
authors.lastname: Porcher
authors.forename: Chaolun
authors.initials: C
authors.lastname: Liang
authors.forename: Fengjuan
authors.initials: F
authors.lastname: Pan
authors.forename: Mingmei
authors.initials: M
authors.lastname: Wu