Center for Individual Nanoparticle Functionality, Department of Physics, Building 312, Technical University of Denmark, DK-2800 Lyngby, Denmark.
Langmuir. 2011 Mar 1;27(5):2058-66. doi: 10.1021/la1042475. Epub 2011 Jan 18.
The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO(4) using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange between the adsorbate and Pt surface atoms (0.45-1.15 V vs RHE). An equivalent electric circuit is proposed to model the Pt(111)/electrolyte interface under ORR conditions within the selected potential window. This equivalent circuit reflects three processes with different time constants, which occur simultaneously during the ORR at Pt(111). Density functional theory (DFT) calculations were used to correlate and interpret the results of the measurements. The calculations indicate that the coadsorption of ClO(4)* and Cl* with OH* is unlikely. Our analysis suggests that the two-dimensional (2D) structures formed in O(2)-free solution are also formed under ORR conditions.
在 0.1 M HClO(4)中，使用电化学阻抗谱研究了 Pt(111)/电解质界面在氧还原反应 (ORR) 期间的特性。在吸附 OH和 O物种发生而吸附物和 Pt 表面原子之间没有明显的位置交换的电位区域内研究了表面（相对于 RHE 的 0.45-1.15 V）。提出了一个等效电路来模拟所选电位窗口内 ORR 条件下的 Pt(111)/电解质界面。该等效电路反映了三个具有不同时间常数的过程，它们在 Pt(111)上的 ORR 过程中同时发生。密度泛函理论 (DFT) 计算用于关联和解释测量结果。计算表明，ClO(4)和 Cl与 OH*的共吸附不太可能发生。我们的分析表明，在无 O(2)溶液中形成的二维 (2D) 结构也在 ORR 条件下形成。
