Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La3+ and Nd3+) in Molten Salts
文献类型：期刊论文
| 作者 | Jiang, Shilin; Lan, Jianhui; Wang, Lin; Liu, Yalan; Zhong, Yuke; Liu, Yichuan; Yuan, Liyong L. -Y.; Zheng, Lirong; Chai, Zhifang; Shi, Weiqun |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2021 |
| 卷号 | 27期号:45页码:11721-11729 |
| 关键词 | RAY-ABSORPTION SPECTROSCOPY SHORT-RANGE STRUCTURE LICL-KCL ELECTROCHEMICAL-BEHAVIOR NEUTRON-DIFFRACTION VIBRATIONAL-MODES BINARY MELTS RAMAN COVALENCY SYSTEMS |
| 英文摘要 | Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La3+ and Nd3+) is explored in molten LiCl-KCl-LiF-LnCl(3) salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln(3+) occur when F- concentration increases, indicating that the F- anions interact with Ln(3+) via substituting the coordinated Cl- anions, and confirm [LnCl(x)F(y)](3-x-y) (y(max)=3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl- and F- anions, which leads to the formation of four distinct Ln(III) species: [LnCl(6)](3-), [LnCl(5)F](3-), [LnCl(4)F(2)](3-) and [LnCl(4)F(3)](4-). Among them, the seven-coordinated [LnCl(4)F(3)](4-) complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, it was concluded that Ln-F interaction is weaker than that between transition metal and F- ions. |
| 源URL | [http://ir.nimte.ac.cn/handle/174433/21760]  |
| 专题 | 中国科学院宁波材料技术与工程研究所 2021专题_期刊论文 |
| 作者单位 | 1.Liu, YL 2.Shi, WQ (corresponding author), Chinese Acad Sci, Lab Nucl Energy Chem, Inst High Energy Phys, Beijing 100049, Peoples R China. |
| 推荐引用方式 GB/T 7714 | Jiang, Shilin,Lan, Jianhui,Wang, Lin,et al. Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La3+ and Nd3+) in Molten Salts[J]. CHEMISTRY-A EUROPEAN JOURNAL,2021,27(45):11721-11729. |
| APA | Jiang, Shilin.,Lan, Jianhui.,Wang, Lin.,Liu, Yalan.,Zhong, Yuke.,...&Shi, Weiqun.(2021).Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La3+ and Nd3+) in Molten Salts.CHEMISTRY-A EUROPEAN JOURNAL,27(45),11721-11729. |
| MLA | Jiang, Shilin,et al."Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La3+ and Nd3+) in Molten Salts".CHEMISTRY-A EUROPEAN JOURNAL 27.45(2021):11721-11729. |
入库方式： OAI收割
来源：宁波材料技术与工程研究所
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