Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2013

Towards understanding the electronic structure of Fe-doped CeO2 nanoparticles with X-ray spectroscopy

Wei-Cheng Wang
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Shih-Yun Chen
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Per-Anders Glans
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Jinghua Guo
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Ren-Jie Chen
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Kang-Wei Fong
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Chi-Liang Chen
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Ching-Lin Chang
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Ting-Shan Chan
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Jin-Ming Chen
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Jyh-Fu Lee
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Chung-Li Dong
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Résumé

This study reports on the electronic structure of Fe-doped CeO2 nanoparticles (NPs), determined by coupled X-ray absorption spectroscopy and X-ray emission spectroscopy. A comparison of the local electronic structure around the Ce site with that around the Fe site indicates that the Fe substitutes for the Ce. The oxygen K-edge spectra that originated from the hybridization between cerium 4f and oxygen 2p states are sensitive to the oxidation state and depend strongly on the concentration of Fe doping. The Ce M4,5-edges and the Fe L2,3-edges reveal the variations of the charge states of Ce and Fe upon doping, respectively. The band gap is further obtained from the combined absorption-emission spectrum and decreased upon Fe doping, implying Fe doping introduces vacancies. The oxygen vacancies are induced by Fe doping and the spectrum reveals the charge transfer between Fe and Ce. Fe3+ doping has two major effects on the formation of ferromagnetism in CeO2 nanoparticles. The first, at an Fe content of below 5%, is that the formation of Fe3+-Vo-Ce3+ introduces oxygen deficiencies favoring ferromagnetism. The other, at an Fe content of over 5%, is the formation of Fe3+-Vo-Fe3+, which favors antiferromagnetism, reducing the Ms. The defect structures Fe 3+-Vo-Ce3+ and Fe3+-Vo-Fe3+ are crucial to the magnetism in these NPs and the change in Ms can be described as the effect of competitive interactions of magnetic polarons and paired ions. This journal is

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Dates et versions

hal-04882887 , version 1 (13-01-2025)

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Wei-Cheng Wang, Shih-Yun Chen, Per-Anders Glans, Jinghua Guo, Ren-Jie Chen, et al.. Towards understanding the electronic structure of Fe-doped CeO2 nanoparticles with X-ray spectroscopy. Physical Chemistry Chemical Physics, 2013, 15 (35), pp.14701-14707. ⟨10.1039/c3cp52054d⟩. ⟨hal-04882887⟩
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