钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究

doi:10.7503/cjcu20160171

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (9): 1701.doi: 10.7503/cjcu20160171

钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究

宗美荣¹, 何辉超², 董发勤^1,²(), 何平², 孙仕勇¹, 刘明学¹, 聂小琴¹

1. 西南科技大学固体废物处理与资源化教育部重点实验室, 绵阳 621010
2. 西南科技大学四川省非金属复合与功能材料重点实验室-省部共建国家重点实验室培育基地, 绵阳 621010

收稿日期:2016-03-23 出版日期:2016-09-10 发布日期:2016-08-26
作者简介:联系人简介: 董发勤, 男, 博士, 教授, 主要从事环境友好材料和地球科学方面的研究. E-mail:fqdong@swuat.edu.cn
基金资助:
国家“九七三”计划项目(批准号: 2014CB846003)、国家自然科学基金(批准号: 41272371)和中国博士后科学基金第59批面上基金(编号: 2016M592698)资助

Electrochemical Electron Transfer and Crystallization Process of Uranium(Ⅵ) in Sodium Salt Solution^†

ZONG Meirong¹, HE Huichao², DONG Faqin^1,^2,^*(), HE Ping², SUN Shiyong¹, LIU Mingxue¹, NIE Xiaoqin¹

1. Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education, Southewest University of Science and Technology, Mianyang 621010, China
2. State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southewest University of Science and Technology, Mianyang 621010, China

Received:2016-03-23 Online:2016-09-10 Published:2016-08-26
Contact: DONG Faqin E-mail:fqdong@swuat.edu.cn
Supported by:
† Supported by the State Key Development Program for Basic Research of China(No.2014CB846003), the National Natural Science Foundation of China(No.41272371) and the Fifty-nine Project was supported by the National Science Foundation for Post-doctoral Scientists of China(No.2016M592698)

摘要/Abstract

摘要：

采用循环伏安法分析钠盐溶液中U(Ⅵ)的电化学行为, 恒电位电化学还原处理U(Ⅵ), 利用交流阻抗谱分析电化学还原反应中的过程动力学特性, 利用X射线衍射、扫描电子显微镜和电子能谱等方法分析了U(Ⅵ)的电化学晶化. 结果表明, 在钠盐溶液中, U(Ⅵ)可通过电化学反应先还原成低价的U(V)并进一步还原为U(Ⅳ), U(Ⅳ)一步氧化为U(Ⅵ), U(Ⅳ)/U(Ⅵ)之间的电化学转化过程受扩散控制, 且U(Ⅵ)的电化学电子转移易受环境pH值的影响; 恒电位还原4 h时, 溶液中U(Ⅵ)的去除率可达90%, U(Ⅵ)的结晶固化产物主要以固态的(UO₂)₆O₂(OH)₈·6H₂O(水铀矿) 和UO₂的形式附着在工作电极上.

关键词: 铀(Ⅵ), 电化学, 电化学阻抗谱, 结晶

Abstract:

Electrochemical beheaviors of uranium(VI) was investigated with cyclic voltammetry and chronoamperometry(CV). The reduction of U(Ⅵ) was analyzed by potentiostatic electrochemical and the kinetics was investigated with electrochemical impedance spectroscopy(EIS). In addition, crystallization of U(Ⅵ) were analyzed by X-ray diffraction(XRD), scanning electron microscopy(SEM) and energy-dispersive spectrometry(EDS). The results indicated that the reduction processes of U(Ⅵ) to U(Ⅳ) was significantly in fluenced by the pH value of solution, with the pH value changed from 3.87 to 4.50, the cyclic voltammetry showed that the reduction of U(Ⅵ) to U(Ⅳ) was in a manner of two-step one-electron process with a diffusion-controlled reaction mechanism. The cyclic voltammetry results presented a constant potential reduction method for removing U(Ⅵ) from aqueous solution, and the reduction efficiency can reach 90%. At a constant potential, U(Ⅵ) mainly crystalized into solid phases in the forms of UO₂ and (UO₂)₆O₂(OH)₈·6H₂O. These results could provide a basis for removing and collecting U(Ⅵ) from solution.

Key words: Uranium(Ⅵ), Electrochemistry, Electrochemical impedance spectroscopy, Crystallization

中图分类号:

O646

TrendMD:

宗美荣, 何辉超, 董发勤, 何平, 孙仕勇, 刘明学, 聂小琴. 钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究. 高等学校化学学报, 2016, 37(9): 1701.

ZONG Meirong, HE Huichao, DONG Faqin, HE Ping, SUN Shiyong, LIU Mingxue, NIE Xiaoqin. Electrochemical Electron Transfer and Crystallization Process of Uranium(Ⅵ) in Sodium Salt Solution^†. Chem. J. Chinese Universities, 2016, 37(9): 1701.

图/表 10

Fig.1 Absorbance spectra of ultra-pure water(a), 0.10 mol/L NaCl(b), 0.10 mol/L NaCl+100 mg/L U(Ⅵ)(c) complexing with arsenazo Ⅲ(A) and linear relationship between Abs. and cU(Ⅵ)(B)

Fig.2 Cyclic voltammogram of FTO electrode in 0.10 mol/L NaCl(solid line) and 1.0 mmol/L U(Ⅵ) + 0.10 mol/L NaCl(pH=3.87)(dotted line) at 25 mV/s

Fig.3 Cyclic voltammogram of FTO electrode in 1 mmol/L U(Ⅵ)+0.1 mol/L NaCl(pH=3.87) at diffe-rent scan rates(A) and linear relationship between jop, -jrp and ν1/2(B) (A) Scan rate/(mV·s-1): a. 10; b. 25; c. 50; d. 75; e. 100; f. 250; g. 500; h. 750. (B) a. for peak A(oxidation); b. for peak B(reduction).

Fig.4 Cyclic voltammogram of FTO electrode in 1.0 mmol/L U(Ⅵ)+0.10 mol/L NaCl solution at pH values of 1.5(A), 3.0(B), 4.5(C) and 6.0(D) The scan rate was 25 mV/s.

Table 1 Speciation of U(Ⅵ) at different pH conditions calculated by MINTEQ software*

U(Ⅵ) Species	Percent(%)
U(Ⅵ) Species	pH=1.5	pH=3.0	pH=3.87	pH=4.5	pH=6
U $O 2 2 +$	95.015	93.977	80.362	78.776	—
UO₂Cl⁺	4.816	5.011	4.294	4.209	—
UO₂OH⁺	—	0.251	1.984	2.110	—
(UO₂)₂(OH $) 2 2 +$	—	—	9.794	11.071	0.028
(UO₂)₂OH³⁺	0.015	0.452	3.043	3.171	—
(UO₂)₃(OH $) 4 2 +$	—	0.157	0.196	0.255	0.135
(UO₂)₃OH⁵⁺	—	—	0.192	0.272	21.523
(UO₂)₄OH⁷⁺	—	—	—	—	78.307
UO₂N $O 3 +$	0.131	0.137	0.117	0.115	—
UO₂Cl₂(aq)	0.015	0.016	0.013	0.013	—

Table 1 Speciation of U(Ⅵ) at different pH conditions calculated by MINTEQ software*

U(Ⅵ) Species	Percent(%)
U(Ⅵ) Species	pH=1.5	pH=3.0	pH=3.87	pH=4.5	pH=6
U $O 2 2 +$	95.015	93.977	80.362	78.776	—
UO₂Cl⁺	4.816	5.011	4.294	4.209	—
UO₂OH⁺	—	0.251	1.984	2.110	—
(UO₂)₂(OH $) 2 2 +$	—	—	9.794	11.071	0.028
(UO₂)₂OH³⁺	0.015	0.452	3.043	3.171	—
(UO₂)₃(OH $) 4 2 +$	—	0.157	0.196	0.255	0.135
(UO₂)₃OH⁵⁺	—	—	0.192	0.272	21.523
(UO₂)₄OH⁷⁺	—	—	—	—	78.307
UO₂N $O 3 +$	0.131	0.137	0.117	0.115	—
UO₂Cl₂(aq)	0.015	0.016	0.013	0.013	—

Fig.5 Amperometric i-t curve of FTO electrode in 1 mmol/L U(Ⅵ)+0.1 mol/L NaCl(pH=3.87) at a constant applied potential of -0.50 V(vs. SCE)(A) and variation of the U(Ⅵ) concentration with electrochemical reduction time(B) with(a) or without(b) N2-purging

Fig.6 Electrochemical impedance spectra of FTO electrode in 1.0 mmol/L U(Ⅵ)+0.10 mol/L NaCl(pH=3.87) at a constant applied potential of -0.50 V(vs. SCE) with or without N2 purging(A) and equivalent circuit for FTO electrode(B)

Table 2 Value of the elements in equivalent circuit fitted by the Nyquist plot*

Sample	R_s(Ω)/error(%)	CPE1-T(F)/error(%)	CPE1-P(F)/error(%)	R_ct(Ω)/error(%)
Without N₂-purging	92.56/0.67	5.99×10^-5/1.98	0.96/0.50	6340/6.02
With N₂-purging	84.56/0.98	7.10×10^-5/2.94	0.94/0.75	4765/7.57

Fig.7 Photographs of FTO electrode after different time i-t measurements in 1.0 mmol/L U(Ⅵ)+0.10 mol/L NaCl(pH=3.87) at a constant applied potential of -0.50 V(vs. SCE) with N2-purging(A) and XRD pattern of FTO electrode before and after electrochemical reduction of U(Ⅵ) solution(B)

Fig.8 SEM images(A, B) and EDS spectra(C, D) of FTO electrode after electrochemical reduction in U(Ⅵ) solution for 4 h (C) and (D) are the EDS spectra of the framed area in (A) and (B), respectivery.

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钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究

Electrochemical Electron Transfer and Crystallization Process of Uranium(Ⅵ) in Sodium Salt Solution^†

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钠盐溶液中U(Ⅵ)的电化学电子转移与晶化研究

Electrochemical Electron Transfer and Crystallization Process of Uranium(Ⅵ) in Sodium Salt Solution†

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Electrochemical Electron Transfer and Crystallization Process of Uranium(Ⅵ) in Sodium Salt Solution^†