几种典型的电化学振荡体系研究
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摘要
电化学振荡的深入研究，对于认识电化学振荡现象，发展电极过程动力学，丰富非平衡态、非线性动力学的研究内容，具有重要的科学意义。
本论文从电极过程动力学分类的角度，研究了几种典型的电化学振荡体系，包括电化学反应(电荷传递)分别与表面吸脱附、表面相变和液相传质偶合。
1．C_1有机小分子在Pt／Sb、Pt／Bi修饰电极上电势振荡行为的研究
在采用不可逆吸附方法制得的Pt／Sb修饰电极上研究甲酸、甲醛和甲醇的电化学行为及振荡特征时发现：锑吸附原子能较大地增强Pt对甲酸和甲醛的催化活性，但对甲醇的电氧化起阻碍作用。同时，电化学振荡特征发生改变，但与电催化活性并不呈正相关。振荡变化的原因是由于锑的介入改变了双途径机理的两平行反应的份额，导致体系的正、负反馈的相对强度也随之改变，进而影响了二者的动力学匹配性，并最终导致振荡特征的变化。循环伏安判据能很好地解释所观察到的实验现象。甲酸在欠电位沉积的Pt／Bi修饰电极上的电化学行为及振荡特征与其在Pt／Sb电极上非常相似。
2．金电极在HCl溶液中电溶解电流振荡的现场拉曼光谱研究
采用拉曼光谱测得金溶解过程中出现的Au—Cl~-、AuCl_4~-、Au—O(H)键的振动谱带，扩散层中AuCl_4~-的浓度空间分布以及在电流振荡过程中AuCl_4~-暂态变化等。实验结果表明：金电极表面氧化膜的形成和与Cl~-络合引起的氧化膜溶解的周期性转变，导致在一非常窄的电势范围产生电流振荡。该体系属于典型的电化学反应与表面相变
偶合的电化学振荡
钝化态的相互转变
。CV曲线中的交叉环在本体系中意味着活化态和
3.103一还原过程中电势振荡的EQ以的研究
首次利用EQCM对扩散层粘、密度变化的响应特征，研究了103-
还原中伴随周期性析氢而产生电势振荡的机理。现场检测结果清楚地
证实了振荡过程中所涉及的主要步骤有:①扩散控制下的103一表面浓
度的还原耗尽;②氢气在电极表面的形成、聚集和析出;③析氢引
起的对流使103一的表面浓度重新恢复等。我们的研究表明扩散层的粘、
密度变化的同步检测可为研究本类振荡机理提供关键的有效信息。实
验结果证明:本体系属于典型的电化学反应与传质步骤(液相传质)
相偶合的电化学振荡。
The profound study on electrochemical oscillations has important scientific meaning for recognizing the oscillatory phenomena, developing the electrode processes and richening the research content of the non-equilibrium and nonlinear dynamic. From the viewpoint of electrode processes, several typical electrochemical oscillatory systems have been studied in this paper, including electrochemical reactions coupled with surface ad/desorption, phase transition and liquid mass transfer.
1.Potential oscillatory behaviors on antimony-modified and bismuth-modified platinum electrodes for the electrocatalytic oxidation of one-carbon organic molecules.
Electrochemical behaviors and oscillatory characteristics for the oxidation of one-carbon organic molecules on Pt/Sb electrodes are investigated. We found that with the increase of sb, the electrocatalytic activity increases for the oxidation of HCOOH and HCHO, but decreases for the oxidation of CH3OH. No a positive correlation was found between oscillation and electrocatalytic activity. A plausible explanation is given here. The presence of Sb adatom affects the dual path parallel reactions on Pt in different extents, and thus changes the relative strength of the positive and negative feedbacks on the Pt, leading to the change of oscillatory characteristics. CV criterion explains the experimental results well. The results of formic acid oxidation on. Bi-modified electrodes are similar to those on Pt/Sb electrodes.
2.In situ Raman spectroscopic studies on the current oscillations during gold electrodissolution in HC1 solution
Raman spectroscopy has been used for investigating the gold oscillatory electrodissolution processes in a 2 mol dm-3HCl solution. The
spatial profile of AuCl4- concentration in the diffusion layer, and the temporal evolution of AuCl4- during the current oscillations have all been measured in situ by a confocal Raman spectroscope. These experimental results indicate that the transition between active and passive states of gold accounts for the current oscillations in a very narrow potential range. A crossing cycle in the cyclic voltammogram that means a pair of overlapping positive and negative feedbacks corresponds to the active-passive transition. The electrodisslotion of Au is a typical example of oscillations system generating from the coupling of electrochemical reactions with surface phase transition.
3. In situ monitoring of potential oscillations in the reduction of IO3-by electrochemical quartz crystal microbalance The new experimental results that were obtained by in situ EQCM monitoring clearly demonstrate the all key steps involved in the oscillation: the diffusion-limited depletion of IO3- by reduction, the formation, growth and departure of hydrogen bubbles on the surface, and the convection-induced replenishment of IO3- by the hydrogen evolution, our study shows that simultaneous frequency responses to the changes of density and viscosity in the diffusion layer during the oscillation can also provide meaningful and even decisive information on the oscillatory mechanism for the oscillators involving the coupling of electrochemical reactions with diffusion and convection mass transfer.
本论文从电极过程动力学分类的角度，研究了几种典型的电化学振荡体系，包括电化学反应(电荷传递)分别与表面吸脱附、表面相变和液相传质偶合。
1．C_1有机小分子在Pt／Sb、Pt／Bi修饰电极上电势振荡行为的研究
在采用不可逆吸附方法制得的Pt／Sb修饰电极上研究甲酸、甲醛和甲醇的电化学行为及振荡特征时发现：锑吸附原子能较大地增强Pt对甲酸和甲醛的催化活性，但对甲醇的电氧化起阻碍作用。同时，电化学振荡特征发生改变，但与电催化活性并不呈正相关。振荡变化的原因是由于锑的介入改变了双途径机理的两平行反应的份额，导致体系的正、负反馈的相对强度也随之改变，进而影响了二者的动力学匹配性，并最终导致振荡特征的变化。循环伏安判据能很好地解释所观察到的实验现象。甲酸在欠电位沉积的Pt／Bi修饰电极上的电化学行为及振荡特征与其在Pt／Sb电极上非常相似。
2．金电极在HCl溶液中电溶解电流振荡的现场拉曼光谱研究
采用拉曼光谱测得金溶解过程中出现的Au—Cl~-、AuCl_4~-、Au—O(H)键的振动谱带，扩散层中AuCl_4~-的浓度空间分布以及在电流振荡过程中AuCl_4~-暂态变化等。实验结果表明：金电极表面氧化膜的形成和与Cl~-络合引起的氧化膜溶解的周期性转变，导致在一非常窄的电势范围产生电流振荡。该体系属于典型的电化学反应与表面相变
偶合的电化学振荡
钝化态的相互转变
。CV曲线中的交叉环在本体系中意味着活化态和
3.103一还原过程中电势振荡的EQ以的研究
首次利用EQCM对扩散层粘、密度变化的响应特征，研究了103-
还原中伴随周期性析氢而产生电势振荡的机理。现场检测结果清楚地
证实了振荡过程中所涉及的主要步骤有:①扩散控制下的103一表面浓
度的还原耗尽;②氢气在电极表面的形成、聚集和析出;③析氢引
起的对流使103一的表面浓度重新恢复等。我们的研究表明扩散层的粘、
密度变化的同步检测可为研究本类振荡机理提供关键的有效信息。实
验结果证明:本体系属于典型的电化学反应与传质步骤(液相传质)
相偶合的电化学振荡。
The profound study on electrochemical oscillations has important scientific meaning for recognizing the oscillatory phenomena, developing the electrode processes and richening the research content of the non-equilibrium and nonlinear dynamic. From the viewpoint of electrode processes, several typical electrochemical oscillatory systems have been studied in this paper, including electrochemical reactions coupled with surface ad/desorption, phase transition and liquid mass transfer.
1.Potential oscillatory behaviors on antimony-modified and bismuth-modified platinum electrodes for the electrocatalytic oxidation of one-carbon organic molecules.
Electrochemical behaviors and oscillatory characteristics for the oxidation of one-carbon organic molecules on Pt/Sb electrodes are investigated. We found that with the increase of sb, the electrocatalytic activity increases for the oxidation of HCOOH and HCHO, but decreases for the oxidation of CH3OH. No a positive correlation was found between oscillation and electrocatalytic activity. A plausible explanation is given here. The presence of Sb adatom affects the dual path parallel reactions on Pt in different extents, and thus changes the relative strength of the positive and negative feedbacks on the Pt, leading to the change of oscillatory characteristics. CV criterion explains the experimental results well. The results of formic acid oxidation on. Bi-modified electrodes are similar to those on Pt/Sb electrodes.
2.In situ Raman spectroscopic studies on the current oscillations during gold electrodissolution in HC1 solution
Raman spectroscopy has been used for investigating the gold oscillatory electrodissolution processes in a 2 mol dm-3HCl solution. The
spatial profile of AuCl4- concentration in the diffusion layer, and the temporal evolution of AuCl4- during the current oscillations have all been measured in situ by a confocal Raman spectroscope. These experimental results indicate that the transition between active and passive states of gold accounts for the current oscillations in a very narrow potential range. A crossing cycle in the cyclic voltammogram that means a pair of overlapping positive and negative feedbacks corresponds to the active-passive transition. The electrodisslotion of Au is a typical example of oscillations system generating from the coupling of electrochemical reactions with surface phase transition.
3. In situ monitoring of potential oscillations in the reduction of IO3-by electrochemical quartz crystal microbalance The new experimental results that were obtained by in situ EQCM monitoring clearly demonstrate the all key steps involved in the oscillation: the diffusion-limited depletion of IO3- by reduction, the formation, growth and departure of hydrogen bubbles on the surface, and the convection-induced replenishment of IO3- by the hydrogen evolution, our study shows that simultaneous frequency responses to the changes of density and viscosity in the diffusion layer during the oscillation can also provide meaningful and even decisive information on the oscillatory mechanism for the oscillators involving the coupling of electrochemical reactions with diffusion and convection mass transfer.
引文
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