Both cyclic-voltammetry-based and impedance-based experimental criteria thathave been developed recently for the oscil-latory electrochemical systems are critically appraisedwith two typical categories of oscillators....Both cyclic-voltammetry-based and impedance-based experimental criteria thathave been developed recently for the oscil-latory electrochemical systems are critically appraisedwith two typical categories of oscillators. Consistent conclusions can be drawn by the two criteriafor the category of oscillators that involve the coupling of charge transfer mainly with surfacesteps (e.g. ad- and desorption) such as in the electrooxidation of C_1 organic molecules. Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the couplingof charge transfer mainly with mass transfer (e.g. diffusion and convection) such as in theFe(CN)_6^(3-) reduction accompanying periodic hydrogen evolution. The reason is that the negativeimpedance cannot include the feedback information of convection mass transfer induced by thehydrogen evolution. However, both positive and negative nonlinear feedbacks, i. e., thediffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)_6^(3-) surfaceconcentration, that coexist between the bistability, i. e., Fe(CN)_6^(3-) reduction with and withouthydrogen evolution at lower and higher potential sides respectively, are all reflected in thecrossed cyclic voltammo-gram (CCV). It can be concluded that the voltammetry-based criterion (intime domain) is more intuitive, less time-consuming and has a wider range of applications than theimpedance-based one (in frequency domain).展开更多
文摘Both cyclic-voltammetry-based and impedance-based experimental criteria thathave been developed recently for the oscil-latory electrochemical systems are critically appraisedwith two typical categories of oscillators. Consistent conclusions can be drawn by the two criteriafor the category of oscillators that involve the coupling of charge transfer mainly with surfacesteps (e.g. ad- and desorption) such as in the electrooxidation of C_1 organic molecules. Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the couplingof charge transfer mainly with mass transfer (e.g. diffusion and convection) such as in theFe(CN)_6^(3-) reduction accompanying periodic hydrogen evolution. The reason is that the negativeimpedance cannot include the feedback information of convection mass transfer induced by thehydrogen evolution. However, both positive and negative nonlinear feedbacks, i. e., thediffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)_6^(3-) surfaceconcentration, that coexist between the bistability, i. e., Fe(CN)_6^(3-) reduction with and withouthydrogen evolution at lower and higher potential sides respectively, are all reflected in thecrossed cyclic voltammo-gram (CCV). It can be concluded that the voltammetry-based criterion (intime domain) is more intuitive, less time-consuming and has a wider range of applications than theimpedance-based one (in frequency domain).
