Structure and Optical Property of Pr2O3 Powder Prepared by Reduction

doi:10.15541/jim20220754

Abstract

Abstract:

As an important raw material for synthesis of phosphor and laser gain medium, the sesquioxide of praseodymium (Pr₂O₃) receives few attentions due to its susceptibility to change of valence and hygroscopicity in air. Here, the reduction process from Pr₆O₁₁ to Pr₂O₃ and corresponding mechanism in air and Ar/H₂ atmosphere as well as the crystal phases, morphologies, particle sizes and valence states of the two kinds of oxides were investigated. Furthermore, the photoluminescent properties of praseodymium oxide were analyzed in relation to the valence state of praseodymium. The results show that phase transition of Pr₆O₁₁ significantly varied in different atmospheres. Reduction of Pr₆O₁₁ is accelerated in Ar/H₂ atmosphere and Pr₂O₃ can be obtained at 800 ℃. In addition to adsorption in ultraviolet region resulted from transition from valence to conductive band, the Pr₂O₃ containing Pr³⁺ also shows the absorption in visible light band caused by the f→f transition. Pr₆O₁₁ shows strong absorption to UV-Vis wavelengths over 320 nm, which is related to the charge transfer between Pr⁴⁺ and oxygen ion. Wide band in the fluorescence emission spectrum of Pr₂O₃ indicates that the lowest energy level of 4f5d orbital of Pr³⁺ is below ¹S₀. Fluorescence intensity of Pr₆O₁₁ containing Pr⁴⁺ decreases 63% compared to that of Pr₂O₃ at 404 nm, which can be attributed to the energy dissipation between Pr³⁺and Pr⁴⁺. This difference in fluorescence property can be used to analyze Pr valence in ceramics or crystals with high oxygen ion mobility. This research demonstrated that the transformation process and the related property from Pr₆O₁₁ to Pr₂O₃in different atmosphere may promote the application of Pr₂O₃.

Key words: Pr₂O₃, Pr₆O₁₁, optical property

CLC Number:

TQ174

GU Junyi, FAN Wugang, ZHANG Zhaoquan, YAO Qin, ZHAN Hongquan. Structure and Optical Property of Pr₂O₃ Powder Prepared by Reduction[J]. Journal of Inorganic Materials, 2023, 38(7): 771-777.

Figures/Tables 8

Fig. 1 TG-DTA curves of praseodymium oxalate and Pr6O11 in different atmospheres (a) Praseodymium oxalate tested in the air; (b, c) Pr6O11 tested in (b) air and (c) Ar/H2 atmosphere

Fig. 2 XRD patterns of Pr6O11 and Pr2O3

Fig. 3 SEM images of Pr6O11 and Pr2O3 (a, b) SEM images of Pr6O11 at (a) low and (b) high magnification; (c, d) SEM images of Pr2O3 at (c) low and (d) high magnification

Fig. 4 Particle size distributions of (a) Pr6O11 and (b) Pr2O3 powders

Table 1 Specific surface areas of Pr6O11 and Pr2O3

Sample	S_BET/(m²·g^-1)	S_LDPSA/(m²·g^-1)
Pr₆O₁₁	5.8	2.0
Pr₂O₃	1.9	1.5

Fig. 5 Pr3d XPS spectra of Pr6O11 and Pr2O3

Fig. 6 Infrared and UV-Vis spectra of Pr6O11 and Pr2O3 (a) FT-IR spectra; (b) UV-Vis absorption spectra; (c) UV-Vis reflective spectra

Fig. 7 Fluorescence spectra of powders with different Pr4+ concentrations (a) Emission spectra; (b) Excitation spectra

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Structure and Optical Property of Pr₂O₃ Powder Prepared by Reduction

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