Kinetics and Mechanism of Hypophosphite Electrooxidation on a Nickel Electrode

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(PHO-●2),而磷中心自由基(PHO-●2)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.

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-circle, 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.