氯化物体系中La的电化学提取及共沉积Zn-La合金

doi:10.7503/cjcu20170605

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (6): 1145.doi: 10.7503/cjcu20170605

• 研究论文: 无机化学 • 上一篇下一篇

氯化物体系中La的电化学提取及共沉积Zn-La合金

薛云^1,²(), 曹萌¹, 杨雪¹, 徐琰璐², 颜永得², 纪德彬², 马福秋¹

1. 哈尔滨工程大学核科学与技术学院, 核安全与仿真技术国防重点学科实验室
2. 材料科学与化学工程学院, 超轻材料与表面技术教育部重点实验室, 哈尔滨 150001

收稿日期:2017-09-06 出版日期:2018-06-10 发布日期:2018-05-23
基金资助:
国家自然科学基金(批准号: 51574097)、黑龙江省自然科学基金(批准号: LC2016018)、中央高校基本科研业务经费(批准号: HEUCFG201702)、黑龙江省普通高等学校和哈尔滨工程大学青年学术骨干支持计划项目(批准号: 1253G016, HEUCFQ1415)和黑龙江省博士后启动基金(批准号: LBH-Q15019, LBH-Q15020)资助.

Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System^†

XUE Yun^1,^2,^*(), CAO Meng¹, YANG Xue², XU Yanlu², YAN Yongde², JI Debin², MA Fuqiu¹

1. Fundamental Science on Nuclear Safety and Simulation Technology Laboratory, College of Nuclear Science and Technology
2. Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

Received:2017-09-06 Online:2018-06-10 Published:2018-05-23
Contact: XUE Yun E-mail:E-mail: xueyunhrbeu@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21790373), the Science Foundation of Heilongjiang Province, China(No.LC2016018), the Fundamental Research Funds for the Central Universities, China(No.HEUCFG201702), the Foundation for University Key Teacher of Heilongjiang Province and Harbin Engineering University of China(Nos.1253G016, HEUCFQ1415) and the Scientific Research and Special Foundation Heilongjiang Postdoctoral Science Foundation, China(Nos.LBH-Q15019, LBH-Q15020).

摘要/Abstract

摘要：

通过循环伏安、方波伏安和开路计时电位等方法研究了723 K时, La(Ⅲ)在LiCl-KCl和LiCl-KCl-ZnCl₂熔盐体系中Mo电极上的电化学行为. 结果表明, La(Ⅲ)还原为金属La是一步扩散控制的不可逆还原反应. 在LiCl-KCl-ZnCl₂熔盐中, La(Ⅲ)在预先沉积的Zn阴极上欠电位沉积形成4种Zn-La金属间化合物. 在923 K时通过恒电流电解获得Zn-La合金, 通过X射线衍射(XRD)和扫描电子显微镜(SEM)以及附带的能谱仪(EDS)对合金的相组成和微观形貌进行了分析. 采用恒电位电解提取La并用方波伏安曲线检测La(Ⅲ)离子浓度的变化, 电解50 h后, La(Ⅲ)离子浓度接近于零, 提取效率达到99.55%.

关键词: LiCl-KCl熔盐体系, 熔盐电解, 电化学提取La, Zn-La合金, 提取效率

Abstract:

The electrochemical behavior of La(Ⅲ) ions was studied in LiCl-KCl and LiCl-KCl-ZnCl₂ melts on the Mo electrode at 723 K by cyclic voltammetry, square-wave voltammetry and open-circuit chronopotentiometry. The results showed that the reduction of La(Ⅲ) to La(0) is a one-step irreversible reaction controlled by diffusion. In LiCl-KCl-ZnCl₂ solutions, the underpotential deposition of La formed four kinds of Zn-La intermetallic compounds on pre-deposited Zn. Zn-La alloy was obtained by galvanostatic electrolysis at 923 K. The microstructure and micro-zone chemical analysis of Zn-La alloy were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and energy dispersive spectrometry(EDS). Based on the previous electrochemical results, square-wave voltammetry was used to determine the concentration changes of La during potentiostatic electrolysis, the concentration of La(Ⅲ) was close to zero, and the extraction efficiency was 99.55% after potentiostatic electrolysis for 50 h.

Key words: LiCl-KCl melt salt system, Electrolysis in molten salt, Electrochemical extraction of La, Zn-La alloy, Extraction efficiency

中图分类号:

O616

TrendMD:

薛云, 曹萌, 杨雪, 徐琰璐, 颜永得, 纪德彬, 马福秋. 氯化物体系中La的电化学提取及共沉积Zn-La合金. 高等学校化学学报, 2018, 39(6): 1145.

XUE Yun, CAO Meng, YANG Xue, XU Yanlu, YAN Yongde, JI Debin, MA Fuqiu. Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System^†. Chem. J. Chinese Universities, 2018, 39(6): 1145.

图/表 8

Fig.1 Cyclic voltammograms curves on a Mo electrode(S=0.322 cm2) in the LiCl-KCl melt salt sytem before(a) and after(b) the addition of 1.3×10-4 mol/mL LaCl3 at 723 K(scan rate: 0.2 V/s)

Fig.2 Cyclic voltammograms curves of LiCl-KCl-LaCl3(1.3×10-4 mol/mL) melt salt sytem on a Mo electrode(S=0.322 cm2) at different scan rates at 723 KInset: relationship of the cathodic peak current with the square root of the sweep rate.

Fig.3 Square wave voltammogram obtained on a Mo electrode(S=0.322 cm2) in the LiCl-KCl-LaCl3(1.3×10-4 mol/mL) melt salt system at 723 KPulse height: 25 mV; potential step: 1 mV; frequency: 10 Hz.

Fig.4 Open-circuit chronopotentiogram for a Mo electrode(S=0.322 cm2) in the LiCl-KCl-LaCl3(1.3×10-4 mol/mL) melt salt system at 723 K[deposition potential: -2.4 V(vs. Ag/AgCl); deposition time: 70 s]

Fig.5 Cyclic voltammograms curves on a Mo electrode(S=0.322 cm2) in LiCl-KCl-ZnCl2(1.2×10-4 mol/mL)-LaCl3(1.3×10-4 mol/mL) melt salt system at different cathodic limits at 723 K(scan rate: 0.1 V/s)

Fig.6 Square wave voltammogram(A) and open-circuit chronopotentiogram(B) on a Mo electrode in the LiCl-KCl-ZnCl2(1.2×10-4 mol/mL)-LaCl3(1.3×10-4 mol/mL) melt salt system at 723 K(A) Pulse height: 25 mV; potential step: 1 mV; frequency: 10 Hz; (B) deposition potential: -2.4 V(vs Ag/AgCl); deposition time: 30 s.

Fig.7 XRD patterns of the deposits obtained under galvanostatic electrolysis at a Mo electrode in LiCl-KCl-ZnCl2(8.8×10-4 mol/mL)-LaCl3(1.8×10-4 mol/mL) melt salt system at 923 K at 2 A for 2.5 h

Fig.8 Cross-sectional SEM images(A—C) and EDS analysis(D—F) of the deposit obtained by galvanostatic electrolysis at -6.25 A/cm2 for 2.5 h on a Mo electrode in LiCl-KCl-ZnCl2(8.8×10-4 mol/mL)-LaCl3(1.8×10-4 mol/mL) melt salt system at 923 K(A) SEM image; (B) mapping of La; (C) mapping of Zn; (D)—(F) represent points 001, 002, 003 in (A), respec-tively.

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氯化物体系中La的电化学提取及共沉积Zn-La合金

Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System^†

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氯化物体系中La的电化学提取及共沉积Zn-La合金

Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System†

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Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System^†