Citation: WANG Rong, YANG Cheng-Xu, SHI Ying-Guo, SUN Yu-Zeng, LI Guo-Bao, JIN Tou-Nan, QIN Gao-Wu, LIAO Fu-Hui, LIN Jian-Hua. Phase Relationship, Structure and Cationic Distribution of Oxides in the Mn₃O₄-Fe₂O₃ System Synthesized at 1200 ℃[J]. Acta Physico-Chimica Sinica, ;2012, 28(05): 1021-1029. doi: 10.3866/PKU.WHXB201202271 shu

Phase Relationship, Structure and Cationic Distribution of Oxides in the Mn₃O₄-Fe₂O₃ System Synthesized at 1200 ℃

1.
1. State Key Laboratory of Rare Earth Materials Chemistry and Applications, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China;
2. College of Material Science and Engineering, Beijing University of Technology, Beijing 100022, P. R. China;
3. Key Laboratory for Anisotropy and Texture of Materials(Ministry of Education), Northeastern University, Shenyang 110819 , P. R. China

Received Date: 8 December 2011
Available Online: 27 February 2012
Fund Project: 国家重点基础研究发展规划项目(973)(2010CB833103) (973)(2010CB833103)北京市教委重点基金(KM201010005019)资助 (KM201010005019)

A series of oxides in the Mn₃O₄-Fe₂O₃ system have been synthesized at 1200 ℃ in air, followed by quenching to room temperature. Three solid solutions, Mn_3-3xFe_3xO₄ (0.00≤x≤0.278), Mn_3-3xFe_3xO₄(0.291≤x≤0.667), and Mn_2-2xFe_2xO₃ (0.89≤x≤1.00), have been identified by powder X-ray diffraction (XRD). Rietveld refinement of the XRD data show that the solids belong to the hausmannite phase with the space group I4₁/amd, the spinel phase with the space group Fd3m, and the hematite phase with the space group R3c, respectively. Between these are two-phase regions. ⁵⁷Fe Mössbauer spectra indicate that the valence state of Fe in the three solid solutions is +3; in addition, there are two crystallographically independent Fe³⁺ ions in the unit cells of the hausmannite and spinel phases, and one Fe³⁺ in the hematite phase. Analyses of ⁵⁷Fe Mössbauer spectra and X-ray photoelectron spectra (XPS) revealed that a formula of Mn_1-x²⁺Fe_x³⁺[Mn_x³⁺Fe_x³⁺Mn_2-3x³⁺]O₄ describes the cation distribution of both the hausmannite and spinel phases, but that for the hematite phase is Mn_2-2x³⁺Fe_2x³⁺O₃.
- Phase relationship,
- Structure,
- ⁵⁷Fe Mö,
- ssbauer spectroscopy,
- X-ray photoelectron spectroscopy,
- Cation distribution,
- Mn₃O₄
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Phase Relationship, Structure and Cationic Distribution of Oxides in the Mn3O4-Fe2O3 System Synthesized at 1200 ℃

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Phase Relationship, Structure and Cationic Distribution of Oxides in the Mn₃O₄-Fe₂O₃ System Synthesized at 1200 ℃