Electronic Structures and Oxygen Ion Migration Energies of Metal Doped CeO2 Systems：A DFT+U Study

doi:10.6023/A13070686

Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (12): 1668-1675.DOI: 10.6023/A13070686 Previous Articles Next Articles

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金属掺杂的CeO₂体系电子结构和氧离子迁移能的DFT+U研究

贾桂霄^a, 郝文兴^a, 潘飞^a, 杨吉春^a, 章永凡^b

a 内蒙古科技大学材料与冶金学院包头 014010;
b 福州大学化学与化工学院福州 350108

投稿日期:2013-07-01 发布日期:2013-09-16
通讯作者: 贾桂霄 E-mail:guixiao.jia@163.com
基金资助:
受内蒙古自然科学基金（No. 2010BS0805）和教育部“春晖计划”（No. Z2009-1-01050）项目资助.

Electronic Structures and Oxygen Ion Migration Energies of Metal Doped CeO₂ Systems：A DFT+U Study

Jia Guixiao^a, Hao Wenxing^a, Pan Fei^a, Yang Jichun^a, Zhang Yongfan^b

a School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010;
b Department of Chemistry, Fuzhou University, Fujian 350108

Received:2013-07-01 Published:2013-09-16
Supported by:
Project supported by the Natural Science Foundation of Inner Mongolia (No. 2010BS0805) and "Chunhui plan" of the Ministry of Education (Z2009-1-01050).

Doping energies of Ca, Ba, Sm and Zr in CeO₂ systems and influences of dopings on oxygen ion migration energies and vacancy formation energies were studied using DFT and DFT+U methods. The calculated results showed that the doping energies increased with doping cation radius for doped CeO₂ systems without oxygen vacancies, and for doped CeO₂ systems with oxygen vacancies, the doping energies were related to the valence of the doping cations besides their radius. Calculations on electronic structures of various doped CeO₂ systems showed that Fermi level shifted to the high energy in reduced CeO₂, Zr-and Sm-doped CeO₂ systems, however, in Ca-and Ba-doped CeO₂ systems, negative charges due to the substitution of Ca²⁺ and Ba²⁺ with lower chemical valence for Ce⁴⁺ and positive charges due to the formation of oxygen ion vacancy were neutralized, so Fermi level scarcely shifted. Ce³⁺ existed in the reduced CeO₂ system and the Zr-doped CeO₂ system, which would lead to mixed conductivity with ion and electron one, and electron state of Ce³⁺ layed between Ce4f and O2p. However, the reduction of Ce⁴⁺ was restrained in Ca-, Ba-and Sm-doped CeO₂ systems. The migration of an oxygen vacancy was investigated using the nudged elastic band method. The calculated results indicated that a straightforward migration path between two adjacent oxygen sites for oxygen vacancy hopping was obtained. For Ca-, Ba-, Sm-and Zr-doped CeO₂ systems, the migration energies of oxygen ions were smaller than that of CeO₂ system. In these doped CeO₂ systems, the migration energy of oxygen ions for Ba was the smallest and its doping energy are the largest, so Ba was maybe introduced through adding the third class dopant in experiment.

Key words: cerium dioxide, DFT+U, doping energy, vacancy formation energy, ion migration energy

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Jia Guixiao, Hao Wenxing, Pan Fei, Yang Jichun, Zhang Yongfan. Electronic Structures and Oxygen Ion Migration Energies of Metal Doped CeO₂ Systems：A DFT+U Study[J]. Acta Chimica Sinica, 2013, 71(12): 1668-1675.

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金属掺杂的CeO₂体系电子结构和氧离子迁移能的DFT+U研究

Electronic Structures and Oxygen Ion Migration Energies of Metal Doped CeO₂ Systems：A DFT+U Study

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金属掺杂的CeO2体系电子结构和氧离子迁移能的DFT+U研究