Pt基催化劑表面氫氧電催化反應(yīng)的理論計(jì)算研究
[Abstract]:Hydrogen-oxygen electrocatalytic reaction is an important reaction in hydrogen energy system. Its thermodynamics and kinetics directly affect the energy efficiency and power density of hydrogen production and fuel cell. In the past decade, theoretical calculations based on quantum chemistry have been widely used in the design of electrocatalysts and the study of electrocatalytic reaction mechanism. Based on the results of literature, this paper introduces the results and understandings obtained in the theoretical calculation of surface hydrogen and oxygen electrocatalytic reactions of Pt catalysts in recent years. In the study, the adsorption structure, coverage and the mechanism of reaction path and kinetics of the reaction intermediates were analyzed. The results show that the adsorption characteristics of the reaction intermediates not only affect the activation energy of the reaction control steps, but also affect the surface reaction rate by changing the structure and quantity of the active sites of the surface reaction. For the Pt based catalyst near the peak of the volcano, the calculated adsorption energy is not enough to predict the activity of the catalyst accurately. The influence of the coverage of adsorbate and the adsorption structure must be considered. On the basis of this understanding, a micro kinetic model was established according to the relationship between the free energy and rate of surface reaction and the adsorption energy, coverage degree and electrode potential of the key intermediates. The electrochemical adsorption isotherms of the key adsorbed intermediates on the catalyst surface were obtained by using density functional theory (the relationship between the adsorption structure and the coverage degree and the electrode potential), and the reactive sites, reaction paths and kinetics were determined. The relationship curve between catalytic activity and adsorption energy was constructed, the surface structure and size effect of catalyst were predicted, and some important experimental results were explained.
【作者單位】: 湖北省化學(xué)電源重點(diǎn)實(shí)驗(yàn)室武漢大學(xué)化學(xué)與分子科學(xué)學(xué)院;
【基金】:國家自然科學(xué)基金(編號(hào):21673163,21073137) 國家重點(diǎn)基礎(chǔ)研究發(fā)展計(jì)劃(編號(hào):2012CB932800)資助項(xiàng)目
【分類號(hào)】:O643.36
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