氢氧化钠水溶液体系中金属铬的电化学氧化过程

doi:10.13208/j.electrochem.190710

电化学（中英文） ›› 2020, Vol. 26 ›› Issue (3): 413-421. doi: 10.13208/j.electrochem.190710

氢氧化钠水溶液体系中金属铬的电化学氧化过程

韩平¹^,²^,³, 冯海涛¹^,²^*(), 董亚萍¹^,², 田森¹^,²^,³, 张波¹^,², 李武¹

1. 中国科学院青海盐湖研究所,中国科学院盐湖资源综合高效利用重点实验室,西宁 810008
2. 青海省盐湖资源开发工程技术研究中心,西宁 810008
3. 中国科学院大学,北京 100049

收稿日期:2019-07-10 修回日期:2019-12-16 出版日期:2020-06-28 发布日期:2019-12-18
通讯作者: 冯海涛 E-mail:03fht@163.com
基金资助:
青海省科技厅基础研究项目（No. 2017-ZJ-786）和青海省重大科技专项（No. 2016-GX-A10）资助

Electrochemical Oxidation of Metal Chromium in odium Hydroxide Aqueous Solution

HAN Ping¹^,²^,³, FENG Hai-tao¹^,²^*(), DONG Ya-ping¹^,², TIAN Sen¹^,²^,³, ZHANG Bo¹^,², LI Wu¹

1. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China
2. Qinghai Engineering and Technology Research Center of Salt Lake Resources Development, Xining 810008, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-07-10 Revised:2019-12-16 Published:2020-06-28 Online:2019-12-18
Contact: FENG Hai-tao E-mail:03fht@163.com

摘要/Abstract

摘要：

铬铁电氧化溶出技术是一种全新的制备铬酸钠的方法,具有反应条件温和、过程可控、工艺环保等优点,然而金属铬在NaOH水溶液中的电化学氧化过程尚不明确. 本文采用循环伏安法（CV）和阳极极化法（LSV）对金属铬在NaOH水溶液中的电化学氧化过程进行研究. 使用EDS、SEM、XRD和XPS对电解前后的金属铬表征,判断中间物的产生,使用紫外可见分光光度计验证电解液中生成了铬酸钠. 结果表明,金属铬和中间产物Cr(OH)₃可能依次发生电化学氧化直接生成Na₂CrO₄,阳极极化为金属铬的活化. 随着NaOH溶液浓度的增加,Cr(OH)₃和Na₂CrO₄的生成量在增加,金属铬电化学氧化制备铬酸钠的适宜条件为碱浓度≥ 2 mol·L^-1,阳极电势≥ 1.6 V（vs. SCE）.

关键词: 金属铬, NaOH水溶液, 电化学氧化, 循环伏安, 阳极极化

Abstract:

Ferrochrome electrolysis technology is a novel method for preparing sodium chromate (Na₂CrO₄). Although the method performs well at soft reaction conditions, controllable process, environmentally friendly production process, etc., the electrochemical oxidation process of metal chromium in NaOH aqueous electrolyte is still unclear. At present, there are few research articles about specific electrochemical oxidation of metal chromium in NaOH aqueous electrolyte. It is, therefore, meaningful to carry out the research in electrochemical oxidation mechanism of chromium. The electrochemical oxidation of metal chromium in 0.01 mol·L^-1 ~ 10 mol·L^-1 NaOH aqueous electrolytes at 20 °C was studied by cyclic voltammetry (CV, Scan rate: 100 mV·s^-1) and linear sweep voltammetry (LSV, Scan rate: 1 mV·s^-1) through controlling the potential range. The working electrode (WE) was a chromium rod, the counter electrode (CE) was a platinum sheet, and the reference electrode (RE) was a saturated calomel electrode (SCE). EDS, SEM, XRD and XPS were used to characterize the metal chromium before and after the electrolysis to determine intermediate during electrochemical oxidation. Ultraviolet-visible (UV) spectrophotometer was used to analyze the electrolyte solution after the electrolysis to confirm the formation of Na₂CrO₄. The results indicated that Cr(0) and Cr(OH)₃ might undergo electrochemical oxidations in sequence to directly form Na₂CrO₄. When the anode potential was negative, chromium generated Cr(OH)₃ film through electrochemical oxidation, while hydroxide ions (OH^-) underwent electrochemical oxidation to form oxygen. On the othere hand, when the anode potential was positive, two electrochemical reactions: (1) Cr(0) → Cr(VI); (2) Cr(OH)₃ → Cr(VI) took place. Thus, the anodic polarization included activation of Cr(0). The dissolution reaction of chromium was stimulated by OH^- at a higher concentration of NaOH aqueous solution. Futhremore, the amounts of Cr(OH)₃ and Na₂CrO₄ formed were increased with the increased concentration of NaOH aqueous solutions. At the same time, a large amount of oxygen was deposited on the anode electrode surface with the alkaline concentration ≥ 2 mol·L^-1 and anodic potential ≥ 1.6 V (vs. SCE).

Key words: metal chromium, NaOH aqueous solution, electrochemical oxidation, cyclic voltammetry, anodic polarization

中图分类号:

O646
TQ151

韩平, 冯海涛, 董亚萍, 田森, 张波, 李武. 氢氧化钠水溶液体系中金属铬的电化学氧化过程[J]. 电化学（中英文）, 2020, 26(3): 413-421.

HAN Ping, FENG Hai-tao, DONG Ya-ping, TIAN Sen, ZHANG Bo, LI Wu. Electrochemical Oxidation of Metal Chromium in odium Hydroxide Aqueous Solution[J]. Journal of Electrochemistry, 2020, 26(3): 413-421.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.190710

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I3/413

图/表 8

图1

图2

图3

图4

图5

图6

图7

图8

参考文献 22

[1]	Zhang B( 张波). Electrochemical oxidation and reduction of chromium in aqueous solution & preparation of chromium materials[D]. Beijing: Qinghai Institute of Salt Lakesl(Chinese Academy of Sciences), 2017.
[2]	Ding Y( 丁翼), Ji Z( 纪柱). Production and application of chromium compounds[M]. Beijing: Chemical Industry Press( 化学工业出版社), 2002.
[3]	Peng Z D( 彭忠东), Hu G H( 胡国华). A roasting method to prepare chromate from carbon ferrochrome: China, 200910044609.8[P]. 2011-05-04.
[4]	Wang J L, Hu G R, Peng Z D, et al. Novel method to prepare sodium chromate from carbon ferrochrome[J]. Transactions of Nonferrous Metals Society of China, 2015,25(11):3820-3826. doi: 10.1016/S1003-6326(15)64026-2 URL
[5]	Zhang S L( 张树龙). Research progress of cleaner production technology of chromate[J]. Inorganic Chemicals Industryl( 无机盐工业), 2014,46(2):6-9.
[6]	Feng H T( 冯海涛), Liang J( 梁健), Zheng Z L( 郑竹林), et al. Equipment and method for preparing sodium chromate aqueous electrolyte by electrolysis: China, 2013105251656[P]. 2013-10-30.
[7]	Feng H T( 冯海涛), Li B( 李波), Dong Y P( 董亚萍), et al. Equipment and method for preparing potassium chromate aqueous electrolyte by electrolysis: China, 2013106746783[P]. 2013-12-11.
[8]	El-Basiouny M S, Haruyama S. The Polarization behavior of chromium in acidic sulphate solutions[J]. Corrosion Science, 1977,17(5):405-414. doi: 10.1016/0010-938X(77)90030-0 URL
[9]	Gerretsen J H, De Wit J H W. An investigation of the passivation and breakdown of passivity of chromium by cyclic voltammetry and ellipsometry[J]. Corrosion Science, 1990,30(11):1075-1084. doi: 10.1016/0010-938X(90)90057-C URL
[10]	Armstrong R D, Henderson M. The transpassive dissolution of chromium[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1971,32(1):1-11.
[11]	Keddam M, Mattos O R, Takenouti H. Mechanism of anodic dissolution of iron-chromium alloys investigated by electrode impedances—I. Experimental results and reaction model[J]. Electrochimica Acta, 1986,31(9):1147-1158.
[12]	Keddam M, Mattos O R, Takenouti H. Mechanism of anodic dissolution of iron-chromium alloys investigated by electrode impedances—II. Elaboration of the reaction model[J]. Electrochimica Acta, 1986,31(9):1159-1165. doi: 10.1016/0013-4686(86)80128-1 URL
[13]	Ye C Q( 叶陈清), Hu R G( 胡融刚), Hou R Q( 侯瑞青), et al. Localized corrosion behavior of sensitized 304 stainless steel by scanning reference electrode technique[J]. Journal of Electrochemistryl( 电化学), 2013,19(6):507-511.
[14]	Liu M L, Aiello A, Xie Y S, et al. The effect of shortrange order on passivation of Fe-Cr alloys[J]. Journal of The Electrochemical Society, 2018,165(11):C830-C834.
[15]	Kirchheim R, Heine B, Fischmeister H, et al. The passivity of iron-chromium alloys[J]. Corrosion Science, 1989,29(7):899-917.
[16]	Agrawal A K, Sheth K G, Poteet K, et al. The polarization behavior of Fe-Ni-Cr alloys in concentrated sodium hydroxide solutions in the temperature range 25^oC to 150 °C [J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1972,119(12):1637-1644.
[17]	Knoedler R, Heusler K E. Mechanism of oxidation of chromium to chromate[J]. Electrochimica Acta, 1972,17(2):197-212.
[18]	Jia Z( 贾铮), Dai C S( 戴长松), Chen L( 陈玲). Electrochemical measurement methods[M]. Beijing: Chemical Industry Press( 化学工业出版社), 2006: 144-146.
[19]	Zha Q X( 査全性), Lu J T( 陆君涛), Luo D M( 罗道明), et al. Introductory of electrode kinetics(CENDL-2)[M]. Beijing: Science Press( 科学出版社), 1987: 325.
[20]	Szép, I C. Chemical processing of thin chromium films[J]. Thin Solid Films, 1991,205(1):101-105.
[21]	Wei B M( 魏宝明). Metals corrosion theory and application[M]. Beijing: Chemical Industry Press( 化学工业出版社), 1996: 123.
[22]	Desimoni E, Malitesta C, Zambonin P G, et al. An X-ray photoelectron spectroscopic study of some chromium-oxygen systems[J]. Surface and Interface Analysis, 1988,13(2/3):173-179. doi: 10.1002/(ISSN)1096-9918 URL

氢氧化钠水溶液体系中金属铬的电化学氧化过程

Electrochemical Oxidation of Metal Chromium in odium Hydroxide Aqueous Solution

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 22

相关文章 15

Metrics

[1]	王昊, 曹晓舟, 薛向欣. 锑在氯化胆碱-乙二醇低共熔溶剂中的电沉积研究[J]. 电化学（中英文）, 2022, 28(4): 2103071-.
[2]	应方, 许珊珊, 许燕冰, 梁苗苗, 李剑锋. Fe₃O₄磁性纳米颗粒催化电化学降解土霉素的研究[J]. 电化学（中英文）, 2022, 28(4): 2107141-.
[3]	蔡雪凡, 孙升. 多孔电极电池的循环伏安法模拟[J]. 电化学（中英文）, 2021, 27(6): 646-657.
[4]	邢逸飞, 李娜, 温晓芳, 韩宏彦, 崔敏, 张聪, 任聚杰, 籍雪平. 基于取代型多酸复合材料的多巴胺电化学检测[J]. 电化学（中英文）, 2020, 26(6): 890-899.
[5]	郭佳瑶, 陈煅, 张杰, 詹东平. 法拉第吸脱附偶联过程循环伏安行为的有限元分析[J]. 电化学（中英文）, 2020, 26(2): 281-288.
[6]	刘江, 颜晓敏. 直接碳固体氧化物燃料电池[J]. 电化学（中英文）, 2020, 26(2): 175-189.
[7]	李明雪, 史杭, 刘佳, 张檬, 周剑章, 吴德印, 田中群. 金电极上偶氮腺嘌呤的电化学行为研究[J]. 电化学（中英文）, 2019, 25(6): 651-659.
[8]	凌云, 汤儆, 刘国坤, 宗铖. 暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程[J]. 电化学（中英文）, 2019, 25(6): 731-739.
[9]	M. Rostom Ali, S Sankar Saha, Md Ziaur Rahman. 共晶基离子液体的钴电化学沉积[J]. 电化学（中英文）, 2018, 24(5): 546-554.
[10]	董鹏飞，李娜，赵海燕，崔敏，张聪，任聚杰，藉雪平. Keggin 型磷钨酸盐修饰碳糊电极传感多巴胺的研究[J]. 电化学（中英文）, 2018, 24(5): 555-562.
[11]	黄帅帅，刘诚，金磊，杨防祖，田中群，周绍民. 玻碳电极表面复合配位银电结晶机理研究[J]. 电化学（中英文）, 2018, 24(4): 344-350.
[12]	秦建新，林峰，刘文平，陈超，任孟德. 酸性溶液中Fe²⁺ /Fe³⁺相互转换对电极还原行为的影响[J]. 电化学（中英文）, 2017, 23(6): 702-707.
[13]	M. Rostom Ali, R. K. Biswas, Md. Golam Zakaria. 海沙钛铁矿在硫酸溶液中的电化学溶解研究[J]. 电化学（中英文）, 2017, 23(4): 420-428.
[14]	黄先杰，闫慧，黄帅帅，杨防祖，田中群，周绍民. 玻碳电极表面因瓦合金的电化学成核机理[J]. 电化学（中英文）, 2017, 23(1): 7-12.
[15]	郑艳洁，姚宏，翁少煌，彭花萍，龚仕文，黄莉，戴强，林新华. 硫酸特布他林在聚铬黑T修饰电极上的电化学行为及其测定[J]. 电化学（中英文）, 2016, 22(6): 617-623.