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离子液体添加剂[BMIM]HSO4对锌电积过程析氧反应动力学的影响
引用本文:张启波,华一新.离子液体添加剂[BMIM]HSO4对锌电积过程析氧反应动力学的影响[J].物理化学学报,2011,27(1):149-155.
作者姓名:张启波  华一新
作者单位:Key Laboratory of Ionic Liquids Metallurgy, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, P. R. China
基金项目:国家自然科学基金,高等学校博士学科点专项科研基金
摘    要:研究了1-丁基-3-甲基咪唑硫酸氢盐(BMIM]HSO4)离子液体对锌电积过程析氧反应的影响. 研究工作借助于动电位极化, 电化学阻抗谱, 扫描电镜和X射线衍射等测试技术. 动电位极化曲线及对应的动力学参数分析表明, BMIM]HSO4对阳极析氧反应具有催化作用,可提高析氧反应速率常数. 电化学阻抗谱数据表明,BMIM]HSO4能显著降低阳极析氧电荷传递电阻,在所研究的1.85-2.10 V电位范围内添加5 mg·L-1 BMIM]HSO4, 电阻值至少降低50%. 此外, 添加剂对阳极表面二次反应具有抑制作用, 其在阳极表面的吸附,阻碍了阴离子的阳极活化位点吸附过程. 电化学测试结果与长时间(120 h)阳极极化后所得阳极表面形貌和结晶取向分析结果相一致. BMIM]HSO4的添加能有效抑制中间产物β-PbO2的形成,促进铅银电极表面大块且疏松多孔α-PbO2的生成,加速阳极析氧的进行.

关 键 词:电化学阻抗谱  锌电积  析氧  离子液体添加剂  表面形貌  
收稿时间:2010-09-30
修稿时间:2010-11-16

Effect of the Ionic Liquid Additive-[BMIM]HSO4 on the Kinetics of Oxygen Evolution during Zinc Electrowinning
ZHANG Qi-Bo,HUA Yi-Xin.Effect of the Ionic Liquid Additive-[BMIM]HSO4 on the Kinetics of Oxygen Evolution during Zinc Electrowinning[J].Acta Physico-Chimica Sinica,2011,27(1):149-155.
Authors:ZHANG Qi-Bo  HUA Yi-Xin
Institution:Key Laboratory of Ionic Liquids Metallurgy, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, P. R. China
Abstract:The effect of the ionic liquid additive 1-butyl-3-methylimidazolium hydrogen sulfate (BMIM]HSO4) on the kinetics of oxygen evolution during zinc electrowinning from an acidic sulfate solution was investigated. We used potentiodynamic polarization, electrochemical impedance spectroscopy, scanning electron microscopy, and X-ray diffraction for this study. Potentiodynamic polarization curves and the corresponding kinetic parameter analysis show that BMIM]HSO, has a catalytic effect on oxygen evolution by stimulating the reaction rate constant. Impedance data reveal that BMIM]HSO4 can markedly reduce the oxygen evolution charge transfer resistance. The addition of 5 mg·L-1 BMIM]HSO4 obviously decreased the resistance value by at least 50% over the studied potential range from 1.85 to 2.10 V. In addition, the results of the impedance measurements also suggest an inhibition effect of BMIM]HSO4 on the secondary reactions and this is due to the adsorption of the additive on the anode surface, which decreased the amount of active sites for anion adsorption. All electrochemical results were corroborated with a morphological and orientation analysis of the anodic surface after 120 h of anodic polarization. The addition of BMIM]HSO, inhibited the generation of the intermediate productβ-PbO2 and it promoted the generation of larger, loose, and porous α-PbO2, which benefited the oxygen evolution reaction.
Keywords:Electrochemical impedance spectroscopy  Zinc electrowinning  Oxygen evolution  lonic liquid additive  Surface morphology
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