甲酸Pt电极电化学氧化体系中时间自组织导致的可利用功耗失

在电极化学反应步骤为控制步骤的条件下,对甲酸阳极氧化体系中出现的电化学振荡的阈值及跨越阈值后状态演化的极限环路径进行了系统动力学计算.同时,根据非平衡电极过程的耗散-涨落理论,进一步对跨越振荡阈值前后的临界区与电化学震荡区的极化曲线及功耗谱进行了随机热力学分析计算.研究结果表明,跨越临界区后单位电化学反应功耗谱出现突降...

Useful Power Loss Led by Temporal Self-organization Appearing in Electro-chemical Oxidation System of Formic Acid on Pt-electrode

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.