【作者】 张瑞林；

【导师】 李学良；

【作者基本信息】 合肥工业大学 ， 应用化学， 2003， 硕士

【摘要】 对电化学振荡行为的研究，可以加深我们对电极反应过程机理的认识；对电化学复杂振荡的耦合及同步的研究，则能使我们了解同一电解池中两个研究电极之间如何通过相互作用而形成不同的振荡行为；而对电化学复杂振荡的混沌控制研究，则可以丰富化学与混沌学的交叉研究，对改善电化学反应也很有帮助。铜作为阳极在电溶解过程中能产生丰富复杂的振荡行为，近年来，针对Cu／H₃PO₄体系的研究很多，但对铜阳极溶解过程机理的认识还有待于加强添加物对振荡行为影响的研究，H₂SO₄作为一类特殊的添加剂，对H₃PO₄体系中铜阳极溶解电流振荡的影响尚未见报道。为此，本论文研究了铜阳极在磷酸-硫酸混合溶液中的电流振荡行为。本论文采用线性电位扫描法，通过改变扫描速度、反应温度、串入外电阻以及采用不同形状的电极（环电极与线电极）进行实验。并着重探讨了H₂SO₄作为添加剂对铜阳极电溶解所产生振荡行为的影响。发现振荡的产生是电极表面膜的生成，溶解与一定液相传质作用耦合的结果。另外，发现随着添加剂H₂SO₄含量的增大，电流振荡先增强后逐渐减弱。通过恒电位方法，在实验中观察到小幅振荡、周期振荡、混合振荡、准周期振荡等行为。发现，相对于没有添加剂的情况而言，适量加入添加剂H₂SO₄可以使振荡形式更丰富。利用延迟反馈控制法对铜阳极在磷酸-硫酸溶液中所产生的复杂电化学振荡行为进行控制，研究表明，延迟反馈控制法应用于上述体系是行之有效的。我们在实验中实现了将混沌振荡控制为周期运动，将周期-1振荡控制为周期-2、周期-4振荡的形式。我们还研究了延迟时间和控制因子对控制效果的影响。最后我们研究了双铜电极振荡行为的耦合作用及同步现象，结果表明，两铜电极的振荡互相影响，可以形成同相，锁相等同步行为。物质转移作用对同相同步的形成起决定性作用。添加剂H₂SO₄的适量加入，使得1：1形式同步较多。更多还原

【Abstract】 The study of electrochemical oscillations can make us know the mechanism of electrochemical reactions and the research of coupling and synchronization of electrochemical oscillations make us realize that different oscillations can be made by two work electrodes acting each other. The study of chaos control in electrochemical oscillations can not only combine the research of chemistry and chaos, but also improve electrochemical reactions. There are abundant oscillations in electrochemical system with copper being the anode. These years, there are many reports of the study of Cu/H3PO4 system. We can know further the mechanism of the anodic dissolution of copper by studying the influence of additives put into the above system. There is no report about the influence of H3PO4, a special additive, on Cu/H3PO4 system. In this paper, the anodic dissolution of copper in phosphoric and sulphuric acid was studied.Through sweep voltammograms, we study the results of changing the rate of sweep, temperature, electrodes of different shapes and connecting a resistance .We pay much more attention to the influence of H2SO4.It is found that the oscillation is the result of the breaking and forming of film coupling with the mass transport. It also shows that the oscillation amplitude increases at first, then decreases gradually with the increase of the amount of H2SO4 addition.We find many types of oscillations during the experiments. Compared with the system without additive, there are more kinds of oscillations with H2SO4 as additive in the experiments.Means of the delay feedback is used to control the chaos in the electrochemical oscillations during the process of the anodic dissolution of copper. The result proved that the method is effective. We control the chaos to period and control the period one to period two and period four. We also study the effect of the control-factors.Last, we study the coupling and synchronization of electrochemical oscillations. The results show that the synchronization is determined by mass transport. With suitable amount of H2SO4 put in the system, there are more 1:1 synchronizations discovered.更多还原