稀土Ce掺杂纳米晶Mn-Mo-Ce氧化物阳极及其选择电催化性能

doi:10.11868/j.issn.1001-4381.2016.001320

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摘要

采用阳极电沉积技术制备纳米晶Mn-Mo-Ce氧化物阳极，利用SEM，EDS，XRD，HRTEM，电化学等检测技术及析氧效率测试方法研究氧化物阳极的纳米结构和选择电催化性能，探讨析氧抑氯选择电催化的机理。结果表明：少量Ce掺杂获得了具有网孔状纳米结构的Mn-Mo-Ce氧化物阳极，该阳极在海水中具有99.51%析氧效率的高效选择电催化性能。由于γ-MnO₂结构特性优先吸附OH^-，抑制Cl^-吸附，OH^-在Mn⁴⁺/Mn³⁺变价电催化作用下完成析氧，实现选择电催化过程；Ce掺杂增加反应活性，促进吸附与放电过程；活性（100）晶面的晶面间距增大促进OH^-的流动和新生O₂的逸出，从纳米形貌效应上实现高效析氧抑氯选择电催化性能。

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	史艳华
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	关学雷

关键词 ： Mn-Mo-Ce氧化物, 稀土掺杂, 阳极电沉积, 选择电催化

Abstract：

The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO₂, the OH^- ion is preferentially absorbed, while Cl^- absorption is depressed. OH^- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn⁴⁺/Mn³⁺, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100) crystalline plane promotes OH^- motion and the escape of newborn O₂, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.

Key words： Mn-Mo-Ce oxide rare earth doped anodic deposition selective electro-catalytic

收稿日期: 2016-11-07 出版日期: 2017-09-16

中图分类号:

O646

基金资助:国家自然科学基金资助项目(21171083);辽宁省教育厅一般项目资助项目(L2013154)

通讯作者: 史艳华 E-mail: shiyanhua_2010@163.com

作者简介: 史艳华(1971-), 女, 副教授, 博士, 主要研究方向为材料电化学、纳米材料、腐蚀与防护技术, 联系地址:辽宁省抚顺市望花区丹东路西段一号辽宁石油化工大学机械工程学院(113001), E-mail:shiyanhua_2010@163.com

引用本文:

史艳华, 赵杉林, 王玲, 梁平, 关学雷. 稀土Ce掺杂纳米晶Mn-Mo-Ce氧化物阳极及其选择电催化性能[J]. 材料工程, 2017, 45(9): 72-80.
Yan-hua SHI, Shan-lin ZHAO, Ling WANG, Ping LIANG, Xue-lei GUAN. Nanocrystalline Mn-Mo-Ce Oxide Anode Doped Rare Earth Ce and Its Selective Electro-catalytic Performance. Journal of Materials Engineering, 2017, 45(9): 72-80.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2016.001320 或 http://jme.biam.ac.cn/CN/Y2017/V45/I9/72

Fig.1 不同CeCl₃含量时Mn-Mo-Ce氧化物镀层SEM像
(a)0.000mol·L^-1; (b)0.005mol·L^-1; (c)0.010mol·L^-1; (d)0.020mol·L^-1

Fig.2 不同CeCl₃含量时Mn-Mo-Ce氧化物镀层的FESEM像
(a)0.000mol·L^-1; (b)0.005mol·L^-1; (c)0.010mol·L^-1; (d)0.020mol·L^-1

Table 1 不同CeCl₃含量制备的Mn-Mo-Ce氧化物的成分(质量分数/%)

Fig.3 不同CeCl₃含量时Mn-Mo-Ce氧化物阳极的XRD谱图
(a)0.000mol·L^-1; (b)0.005mol·L^-1; (c)0.010mol·L^-1; (d)0.020mol·L^-1

Fig.4 MnO₂的HR-TEM像及电子衍射花样

Fig.5 Mn-Mo-Ce氧化物的HR-TEM像及电子衍射花样

Table 2 两种氧化物各晶面间距与PDF卡片标准数值对比

Fig.6 Mn-Mo-Ce氧化物的循环伏安曲线

Fig.7 Mn-Mo-Ce氧化物的电化学交流阻抗谱

Table 3 拟合后的电化学参数

Fig.8 CeCl₃含量与析氧效率的关系

Fig.9 析氧过程示意图
(a)Mn⁴⁺(OH^-); (b)(Mn³⁺)OH_ads; (c)(Mn⁴⁺)O_ads; (d)析出氧气

Fig.10 空位和元素掺杂在γ-MnO₂(100) 晶面的投影

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[1]	史艳华, 赵杉林, 梁平, 王玲, 关学雷. pH值对阳极电沉积Mn-Mo氧化物结构与性能的影响[J]. 材料工程, 2016, 44(12): 7-12.
[2]	崔旭梅, 黄载春, 陈孝娥. 稀土元素掺杂TiO₂薄膜的制备及其光学性能研究[J]. 材料工程, 2008, 0(12): 55-57.

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