物理化学学报 >> 2012, Vol. 28 >> Issue (05): 1021-1029.doi: 10.3866/PKU.WHXB201202271

热力学,动力学和结构化学 上一篇    下一篇

1200 ℃合成Mn3O4-Fe2O3体系的物相关系、结构和阳离子分布

王蓉2, 杨承旭1, 时迎国3, 孙玉增1, 李国宝1, 金头男2, 秦高梧3, 廖复辉1, 林建华1   

  1. 1. 北京大学化学与分子工程学院, 北京分子科学国家实验室, 稀土材料化学及应用国家重点实验室, 北京 100871;
    2. 北京工业大学材料科学与工程学院, 北京 100022;
    3. 东北大学材料各向异性与织构教育部重点实验室, 沈阳 110819
  • 收稿日期:2011-12-08 修回日期:2012-02-13 发布日期:2012-04-26
  • 通讯作者: 李国宝,金头男,秦高梧,林建华 E-mail:liguobao@pku.edu.cn; tnjinkim@bjut.edu.cn; qingw@smm.neu.edu.cn; jhlin@pku.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973)(2010CB833103)和北京市教委重点基金(KM201010005019)资助

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

WANG Rong2, YANG Cheng-Xu1, SHI Ying-Guo3, SUN Yu-Zeng1, LI Guo-Bao1, JIN Tou-Nan2, QIN Gao-Wu3, LIAO Fu-Hui1, LIN Jian-Hua1   

  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:2011-12-08 Revised:2012-02-13 Published:2012-04-26
  • Contact: LI Guo-Bao, JIN Tou-Nan, QIN Gao-Wu, LIN Jian-Hua E-mail:liguobao@pku.edu.cn; tnjinkim@bjut.edu.cn; qingw@smm.neu.edu.cn; jhlin@pku.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Project of China (973) (2010CB833103) and Scientific Research Key Program of Beijing Municipal Commission of Education, China (KM201010005019).

摘要: 在空气气氛中1200 ℃温度下合成了Mn3O4-Fe2O3体系的各类样品, 并将其快速淬火到室温. X射线粉末衍射(XRD)分析表明这样得到的该体系样品存在三个固溶体Mn3-3xFe3xO4 (0.00≤x≤0.278), Mn3-3xFe3xO4(0.291≤x≤0.667)和Mn2-2xFe2xO3(0.89≤x≤1.00). X射线粉末衍射数据的结构精修显示它们分别具有I41/amd空间群的黑锰矿结构、Fd3m空间群的尖晶石结构和R3c 空间群的赤铁矿结构. 各固溶体之间都存在两相共存的区域. 57Fe 穆斯堡尔谱数据显示Fe 在各个物相中都是Fe3+, 在黑锰矿和尖晶石中存在两种结晶学环境不同的Fe3+, 而在赤铁矿中只存在一种Fe3+. 结合X射线光电子能谱(XPS)的数据, 可以认为黑锰矿和尖晶石中的阳离子分布可以用分子式Mn1-x2+Fex3+[Mnx3+Fex3+Mn2-3x3+]O4表示, 而赤铁矿为Mn2-2x3+Fe2x3+O3.

关键词: 相关系, 结构, 57Fe穆斯堡尔谱, X射线光电子能谱, 阳离子分布, Mn3O4, Fe2O3

Abstract: 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, Mn3-3xFe3xO4 (0.00≤x≤0.278), Mn3-3xFe3xO4(0.291≤x≤0.667), and Mn2-2xFe2xO3 (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 Mn1-x2+Fex3+[Mnx3+Fex3+Mn2-3x3+]O4 describes the cation distribution of both the hausmannite and spinel phases, but that for the hematite phase is Mn2-2x3+Fe2x3+O3.

Key words: Phase relationship, Structure, 57Fe Mö, ssbauer spectroscopy, X-ray photoelectron spectroscopy, Cation distribution, Mn3O4, Fe2O3

MSC2000: 

  • O641