关键词: 甲酸电化氧化, 电化学耗散, 电化学极化, 不可逆电极过程的时间自组织, 可利用功耗失

Abstract: The research of power loss origining from the dissipation-fluctuation in electro-chemical oscillation appearing in the irreversible electrode processes is of special importance for the extension of applied electro-chemistry. In this paper both the threshold of potential oscillation and the trajactories of limit cyccle beyond it in the electro-chemical oxidation system of formic acid on Pt has beeb analysed and computed by using nonlinear systematical dynamics under the assumption that the electrochemical reaction steps are dominate. Furthermore, by means of the dissipation – fluctuation theory of polarization based on stochastic thermodynamics the polarization curves, as well as the spectrum of power loss in both the critical regime and the temporal self-organization regime have been also obtained. It tunns out that the spectrum of power loss per unit electrochemical reaction will abruptly decrease during the current density (externally controlled ) crossing its threshold (Hopf bifurcation point ). Following with the appearance of the temporal self-organization the average power loss per unit electrochemical reaction per period still increase with the current, however it keeps at a level lower than that before threshold until the current arrives to certain high extent.

Key words: Eletro-chemical oxidation of formic acid, Eletro-chemical dissipation, Eletro-chemical Polarization, Temporal self-organization in irreversible electrode processes, Usful power loss