金属掺杂的CeO2体系电子结构和氧离子迁移能的DFT+U研究

doi:10.6023/A13070686

化学学报 ›› 2013, Vol. 71 ›› Issue (12): 1668-1675.DOI: 10.6023/A13070686 上一篇下一篇

研究论文

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).

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摘要/Abstract

使用DFT和DFT+U方法研究了Ca，Ba，Sm与Zr在CeO₂体系中的掺杂能及其掺杂对缺陷形成能和氧离子迁移能的影响规律. 计算结果表明，对未含有氧离子空位的掺杂体系，掺杂能随着掺杂离子半径的增大而增大；对含有氧离子空位的掺杂体系，掺杂能受到掺杂离子半径和价态的影响；对各种掺杂体系电子结构的研究发现，在还原CeO₂，Zr和Sm掺杂的CeO₂体系中，由于氧空位捕获电子使Fermi能级升高；在碱土金属掺杂的CeO₂体系中，由于Ca²⁺和Ba²⁺取代高价态Ce⁴⁺而产生的负电荷恰恰与氧离子空位产生的正电荷中和，因此Fermi能级几乎没有移动；还原CeO₂和Zr掺杂的CeO₂体系均含有Ce³⁺，其新态位于Ce4f和O2p之间，这将导致CeO₂体系具有离子和电子导电特性；Ca，Ba和Sm的掺杂均抑制了CeO₂体系中Ce⁴⁺的变价. 使用NEB方法对氧离子迁移能进行了研究，且结果表明，氧离子到空位的迁移路径几乎沿一条直线进行；当掺杂Ca，Ba，Sm与Zr时，氧离子迁移能均小于纯CeO₂体系的；在这些掺杂体系中，Ba掺杂的体系氧离子迁移能最小，掺杂能较大，这可能导致在实验中常通过加入第三类掺杂物来引入Ba.

关键词: 二氧化铈, DFT+U, 掺杂能, 缺陷形成能, 离子迁移能

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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贾桂霄, 郝文兴, 潘飞, 杨吉春, 章永凡. 金属掺杂的CeO₂体系电子结构和氧离子迁移能的DFT+U研究[J]. 化学学报, 2013, 71(12): 1668-1675.

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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