还原制备Pr2O3粉体及其结构和光学性能研究

doi:10.15541/jim20220754

无机材料学报 ›› 2023, Vol. 38 ›› Issue (7): 771-777.DOI: 10.15541/jim20220754 CSTR: 32189.14.10.15541/jim20220754

还原制备Pr₂O₃粉体及其结构和光学性能研究

顾军毅¹^,²(), 范武刚², 张兆泉², 姚琴²(), 展红全¹()

1.景德镇陶瓷大学材料科学与工程学院, 景德镇 333403
2.中国科学院上海硅酸盐研究所, 上海200050

收稿日期:2022-12-15 修回日期:2023-01-09 出版日期:2023-02-21 网络出版日期:2023-02-21
通讯作者: 展红全, 教授. E-mail: zhanhongquan@jci.edu.cn;
姚琴, 副研究员. E-mail: yaoqin@mail.sic.ac.cn
作者简介:顾军毅(1997-), 男, 硕士研究生. E-mail: 2020028013@stu.jci.edu.cn
基金资助:
国家重大科技专项基金(2017ZX06002004);国家自然科学基金(52062020)

Structure and Optical Property of Pr₂O₃ Powder Prepared by Reduction

GU Junyi¹^,²(), FAN Wugang², ZHANG Zhaoquan², YAO Qin²(), ZHAN Hongquan¹()

1. School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2022-12-15 Revised:2023-01-09 Published:2023-02-21 Online:2023-02-21
Contact: ZHAN Hongquan, professor. E-mail: zhanhongquan@jci.edu.cn;
YAO Qin, associate professor. E-mail: yaoqin@mail.sic.ac.cn
About author:GU Junyi (1997-), male, Master candidate. E-mail: 2020028013@stu.jci.edu.cn
Supported by:
National Science and Technology Major Project of China(2017ZX06002004);National Natural Science Foundation of China(52062020)

摘要/Abstract

摘要：

镨的倍半氧化物(Pr₂O₃)是合成荧光粉和激光增益介质的重要原料, 由于其易发生镨的变价并在空气中吸水而受到的关注较少。本研究采用不同表征手段研究在空气和在氩氢混合气氛下Pr₆O₁₁还原为Pr₂O₃的过程机理以及两种粉体的物相、微观形貌、粒度及价态等, 并进一步分析以上两种氧化镨的发光特性与镨的价态关系。结果表明: 两种气氛下氧化镨的相变过程显著不同, 还原性的Ar/H₂气氛可以加快Pr₆O₁₁的还原过程, 在800 ℃即可得到Pr₂O₃。含Pr³⁺的Pr₂O₃除了导带到价带跃迁导致的紫外吸收外, 还存在因f→f跃迁引发的可见光波段的吸收, 而Pr₆O₁₁对波长超过320 nm的紫外-可见光有较强吸收, 这与Pr⁴⁺和氧之间电荷转移有关。Pr₂O₃的荧光发射光谱中的宽谱带显示Pr³⁺的4f5d轨道的最低能级在¹S₀之下, 同时含Pr⁴⁺的Pr₆O₁₁在404 nm处的荧光强度降低63%, 这归因于Pr³⁺/Pr⁴⁺之间的能量耗散。这种荧光性能的差异可用于含谱的高氧离子迁移率陶瓷或晶体中Pr的价态分析。本工作研究的Pr₆O₁₁到Pr₂O₃在不同气氛下的转变过程及相关机理性能, 有望推动Pr₂O₃在不同领域的应用。

关键词: Pr₂O₃, Pr₆O₁₁, 光学性能

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

中图分类号:

TQ174

顾军毅, 范武刚, 张兆泉, 姚琴, 展红全. 还原制备Pr₂O₃粉体及其结构和光学性能研究[J]. 无机材料学报, 2023, 38(7): 771-777.

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.

图/表 8

图1 不同气氛下草酸镨和Pr6O11的TG-DTA曲线

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

图2 Pr6O11和Pr2O3的XRD图谱

Fig. 2 XRD patterns of Pr6O11 and Pr2O3

图3 Pr6O11和Pr2O3的SEM照片

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

图4 粉体的粒度分布

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

表1 Pr6O11和Pr2O3比表面积

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

图5 Pr6O11和Pr2O3的Pr3d XPS能谱

Fig. 5 Pr3d XPS spectra of Pr6O11 and Pr2O3

图6 Pr6O11和Pr2O3的红外和紫外-可见光光谱图

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

图7 不同Pr4+浓度粉体的荧光光谱

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

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还原制备Pr₂O₃粉体及其结构和光学性能研究

Structure and Optical Property of Pr₂O₃ Powder Prepared by Reduction

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