物理化学学报 >> 2003, Vol. 19 >> Issue (08): 718-722.doi: 10.3866/PKU.WHXB20030809

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次亚磷酸根在镍电极上的电氧化机理与动力学

曾跃;郑仰存;易建龙;于尚慈;杨春明;李则林   

  1. 湖南师范大学化学系，长沙　410006
  • 收稿日期:2003-01-22 修回日期:2003-03-24 发布日期:2003-08-15
  • 通讯作者: 曾跃 E-mail:zengyue@cs.hn.cn

Kinetics and Mechanism of Hypophosphite Electrooxidation on a Nickel Electrode

Zeng Yue;Zheng Yang-Cun;Yi Jian-Long;Yu Shang-Ci;Yang Chun-Ming;Li Ze-Lin   

  1. Department of Chemistry, Hunan Normal University, Changsha　410006
  • Received:2003-01-22 Revised:2003-03-24 Published:2003-08-15
  • Contact: Zeng Yue E-mail:zengyue@cs.hn.cn

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摘要： 用电化学质谱(EMS)和动力学模型分析等方法研究了次亚磷酸根在镍电极上的电化学氧化机理和动力学.研究表明，次亚磷酸根的电化学氧化是通过从P－H键脱离一个原子H，形成磷中心自由基(PHO2－•)，而磷中心自由基(PHO2－•)进一步进行电化学反应形成最终产物亚磷酸。利用该模型，推导出相关动力学方程并通过与实验数据拟合获得动力学参数.结果表明，该模型能很好地模拟次亚磷酸根在镍电极上的电化学氧化过程.

关键词: 动力学, 机理, 次亚磷酸, 电氧化, 镍电极

Abstract: Kinetics and mechanism of hypophosphite oxidation on a nickel electrode were studied by means of the electrochemical mass spectroscopy (EMS) and kinetic model analysis. In the kinetic model, the electrooxidation of hypophosphite undergoes an H abstraction of hypophosphite from the P－H bond to form the phosphorus-centered radical, PHO2－•,which subsequently is electrochemically reacted with water to form the final product, phosphite. The kinetic equations were derived, and the kinetic parameters were obtained from a comparison of experimental results and the kinetic equations. The process of hypophosphite electrooxidation on a nickel electrode could be well simulated by this model.

Key words: Kinetics, Mechanism, Hypophosphite, Electrooxidation, Nickel electrode