Morphology-Controlled Synthesis of CeO2 Microstructures and Their Room Temperature Ferromagnetism

doi:10.1016/j.jmst.2016.06.018

Abstract

Abstract:

Gear-shape CeO₂ microstructures have been synthesized via a facile hydrothermal method with Ce(NO₃)₃?6H₂O as the cerium source, NH₄HCO₃ as both the precipitator and the carbon source, and cetyltrimethyl ammonium bromide (CTAB) as the surfactant. X-ray diffraction (XRD) inferred that the synthesized CeO₂ microstructures exhibited a fluorite structure. The band gap (E_g) of CeO₂ samples is larger than that of bulk. X-ray photoelectron spectroscopy (XPS) showed that there are plenty of Ce³⁺ ions and oxygen vacancies at the surface of CeO₂ samples. All the synthesized CeO₂ samples exhibited the room temperature ferromagnetism, and the saturation magnetization increases with the increases of lattice parameter and E_g. The room temperature ferromagnetism mechanism of gear-shape CeO₂ is mainly attributed to the influence Ce³⁺ ions.

Key words: Ceria, Controlled synthesis, Ferromagnetism, Hydrothermal method, Nanomaterials

Meng Fanming, Fan Zhenghua, Zhang Cheng, Hu Youdi, Guan Tao, Li Aixia. Morphology-Controlled Synthesis of CeO₂ Microstructures and Their Room Temperature Ferromagnetism[J]. J. Mater. Sci. Technol., 2017, 33(5): 444-451.

Figures/Tables 13

Fig. 1. XRD patterns of the as-synthesized samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 2. Overall SEM images of as-synthesized Ce(CO3)(OH) prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 3. High-magnification SEM images of as-synthesized Ce(CO3)(OH) prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 5. XRD patterns of annealing gear-shape samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 6. SEM images of annealing gear-shape samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 7. Schematic illustration of the formation process of Ce(CO3)(OH) microstructures with different morphologies.

Fig. 8. XPS of Ce3d (a) and O1s (b) core levels spectra of gear-shape CeO2 samples prepared with Ce(NO3)3?6H2O of 4 mmol.

Table 1. Integrated areas of individual XPS peaks of the Ce 3d and O 1s from gear-shape CeO2 sample prepared with Ce(NO3)3?6H2O of 4 mmol

Ce 3d_3/2 ----------------------				Ce 3d_5/2 ----------------				O 1s --------------
u″′	u″	u′	u	v″′	v″	v′	v	Ce⁴⁺-O	Ce³⁺-O
49,391.83	19,757.96	30,474.33	57,303.20	80,149.97	61,001.08	100,853.50	72,896.72	60,263.86	20,349.76

Table 2. Concentrations of Ce3+ and Ce4+ ions and stoichiometry x = [O]/[Ce] of gear-shape CeO2 sample prepared with Ce(NO3)3?6H2O of 4 mmol

[Ce³⁺]	[Ce⁴⁺]	x = [O]/[Ce]^a	x′ = [O1s]/[Ce3d]^b
27.83%	72.17%	1.86	1.78

Fig. 9. Room temperature Raman spectra of gear-shape CeO2 samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 10. UV-Vis absorption spectra and insets plots of (ahv)2 as function of energy of the CeO2 samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Fig. 11. Magnetic hysteresis loops of CeO2 samples prepared with different dosages of Ce(NO3)3?6H2O: (a) 2 mmol, (b) 4 mmol, (c) 6 mmol, (d) 8 mmol.

Table 3. Parameters of Ms, Mr, Hc, lattice parameter, Eg and Ce3+ concentration for CeO2 samples with different dosages of Ce(NO3)3?6H2O

Dosages of Ce(NO₃)₃?6H₂O (mmol)	M_s (×10^-3 emu/g)	M_r (×10^-4 emu/g)	H_c (Oe)	Lattice parameter (nm)	E_g (eV)	Ce³⁺ concentration (%)
2	7.2	8.97	144	0.5420	3.72	—
4	6.1	7.63	166	0.5418	3.70	27.83
6	3.3	5.07	174	0.5415	3.69	—
8	3.0	4.34	97	0.5412	3.57	24.53
Bulk CeO₂	0	0	0	0.5411	3.19	0

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Morphology-Controlled Synthesis of CeO₂ Microstructures and Their Room Temperature Ferromagnetism

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