化学学报 ›› 2002, Vol. 60 ›› Issue (9): 1630-1636. 上一篇    下一篇

研究论文

Ce~(4+)/Ce~(3+)氧化还原体系线性极化与交流阻抗研究

夏熙;刘洪涛;刘洋   

  1. 新疆大学应用化学研究所,乌鲁木齐(830046)
  • 发布日期:2002-09-15

Studies on Ce~(4+)/Ce~(3+) Redox System Using Linear Polarization and Ac Impedance Techniques

Xia Xi;Liu Hongtao;Liu Yang   

  1. Institute of Applied Chemistry, Xinjiang University,Urumchi(830046)
  • Published:2002-09-15

用线性极化法和交流阻抗法研究了新型Ce~(4+)/Ce~(3+)-V~(2+)/V~(3+)氧化 还原电池中Ce~(4+)/Ce~(3+)半电池在不同Ce~(4+)浓度下的电化学行为。得出Ce~ (4+)浓度为0.2 mol/L时,其极化电阻最小,似为理论最佳浓度。实际应用需综合 考虑电池的库仓效率和能量效率等因素,还应尽可能选择较高浓度。测得不同浓度 下的阻抗参数表明,在Ce(SO_4)_2体系处于稳态时,不论是慢扫还是使用低的动频 率,Ce~(4+)的反应都为传质控制;而在体系处于暂态时,则不论是快扫还是使用 高扰动频率,都为传荷控制;而当体系介于稳态和暂态之间时,则为传质和传荷的 混合控制。因而可通过提高传质速率和加入电化学催化剂的方法来提高Ce~(4+) /Ce~(3+)体系的反应速率。

关键词: 极化, 阻抗, 铈化合物, 电催化, 反应速度

The electrochemical behavior of Ce~(4+)/Ce~(3+) couple with various Ce~(4+) concentrations in a novel Ce~(4+)/Ce~(3+)-V~(2+)/V~(3+) redox cell was investigated by linear polarization and ac impedance techniques. The results showed that Ce~(4+) concentration of 0.2 mol/L seemed to be the optimum concentration, at which the polarization resistance was minimized. But as the Coulomb and energy efficiency was considered in a work cell, the Ce~(4+) concentration should be selected as high as possible. When the Ce(SO_4)_2 system was in a steady state, whether the sweep rate or the disturbance frequency was low, the reaction of Ce~(4+) was controlled by mass transfer. On the contrary, when the system was in a transient state, whether high sweep rate or high disturbance frequency was used, the reaction was controlled by charge transfer. While if the system was in a state between steady and transient, the whole reaction was controlled by the combination of charge transfer and mass transfer. Therefore, it would be considerably effective for the improvement of Ce~(4+)/Ce~(3+) reaction to facilitate mass transfer and add electrochemical catalyst.

Key words: POLARIZATION, IMPEDANCE, CERIUM COMPOUNDS, ELECTRO-CATALYSIS, REACTION RATE

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