期刊
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
卷 716, 期 -, 页码 31-44出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2013.09.031
关键词
Density functional theory; Modified Poisson-Boltzmann theory; Platinum electrode; (110)-Step; 1-Dimensional water chain; Reversible potential
资金
- NEDO (New Energy and Industrial Technology Development Organization)
Density functional theory combined with a modified Poisson-Boltzmann theory (DFT-MPB) is applied to H, OH and 0 adsorbate formations on electrified Pt(111) and Pt(332) surfaces in an acid aqueous solution. In this method, the chemical bonds between adsorbates and electrodes are quantitatively described by the DFT, and solvation and electric field effects by the electric double layer are described by combining explicit water adlayer models and modeled continuum electrolyte. The results indicated that H, OH and 0 are bound less strongly to (110)-step on Pt(332) than to terrace on Pt(111) in the electric double layer while the trend is opposite in vacuum. The trend in the electric double layer is consistent with our experimentally-obtained cyclic voltammograms, in which H and (hydr)oxides are formed less easily (at lower and higher potentials, respectively) on Pt(332) than on Pt(111). The small binding energies in the modeled electric double layer mainly stem from destabilizations of adsorbates by the presence of strongly adsorbed water molecules forming 1D H-bond networks on the step. Other effects also are found to contribute to the destabilizations: the strain on the Pt(332) terrace, the confinement by the Pt atoms near the step and the water orientation changes by the formations of adsorbates. (C) 2013 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据