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纳米Ce1-xCoxO2-δ固溶体的水热合成及表征

张国芳1,3, 薛燕峰2, 许交兴1, 邱晓清1, 李广社1, 李莉萍1   

    1. 中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福建350002;
    2. 吉林大学物理学院, 长春 130023;
    3. 中国科学院研究生院, 北京 100049
  • 收稿日期:2006-09-04 修回日期:1900-01-01 出版日期:2007-04-10 发布日期:2007-04-10
  • 通讯作者: 李莉萍

Hydrothermal Synthesis and Characterization of Nanometer Ce1-xCoxO2-δ Solid Solutions

ZHANG Guo-Fang1,3, XUE Yan-Feng2, XU Jiao-Xing1, QIU Xiao-Qing1, LI Guang-She1, LI Li-Ping1*   

    1. State Key Structural Chemistry Laboratory, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China;
    2. College of Physics, Jilin University, Changchun 130023, China;
    3. Graduate School, Chinese Academy of Science, Beijing 100049, China
  • Received:2006-09-04 Revised:1900-01-01 Online:2007-04-10 Published:2007-04-10
  • Contact: LI Li-Ping

摘要: 采用水热方法, 在络合剂及氧化剂的辅助下合成出传统方法难以合成的Ce1-xCoxO2-δ固溶体. XRD结果表明, Ce1-xCoxO2-δ固溶体具有立方萤石结构; 产物的平均粒度约为4 nm. 小半径、低价态Co离子的掺杂导致晶格收缩. 结合XRD和Raman表征结果确定固溶体的固溶限约为x=0.06. 紫外光谱分析结果表明, Co离子以混合价态(+2, +3)存在于CeO2晶格中, 随着钴掺杂量的增大, 带隙逐渐蓝移. 低于固溶限样品的室温体相电导率随着钴含量增大而提高.

关键词: 水热合成, 钴掺杂, 氧空位, 固溶限

Abstract: Using (NH4)2S2O8 and NH4OH as the oxidizer and chelating agent, respectively, Ce1-xCoxO2-δ solid solutions were synthesized under hydrothermal conditions and the optimum preparation parameters were explored. The obtained solid solutions had a cubic fluorite structure, and the average particle size was about 4 nm. The lattice parameter monotonously decreased with increasing the cobalt content. The solubility of x=0.06 was determined by combining XRD and Raman techniques. Cobalt ions are found to be in a mixed valence state of Co2+/ Co3+ in CeO2 lattice. Increasing the cobalt content resulted in a clear blue shift of the absorption threshold edge and an increase of bulk conductivity.

Key words: Hydrothermal synthesis, Cobalt doping, Oxygen vacancy, Solubility

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