The co-adsorption of sulfate, bisulfate and hydrogen on Pt(111) and Au(111) electrodes was studied based on periodic density functional calculations with the aqueous electrolyte represented by both explicit and implicit solvent models. The influence of the electrochemical control parameters such as the electrode potential and pH was taken into account in a grand-canonical approach. Thus, phase diagrams of the stable coadsorption phases as a function of the electrochemical potential and Pourbaix diagrams have been derived which well reproduce experimental findings. We demonstrate that it is necessary to include explicit water molecules in order to determine the stable adsorbate phases as the (bi)sulfate adsorbates rows become significantly stabilized by bridging water molecules.

基于周期性密度泛函计算，采用显式和隐式溶剂模型表示的水性电解质，研究了硫酸根，硫酸氢根和氢在Pt（111）和Au（111）电极上的共吸附。在大经典方法中考虑了电化学控制参数（如电极电势和pH）的影响。因此，已经得到了稳定的共吸附相的相图和电化学势的函数以及Pourbaix图，它们很好地再现了实验结果。我们证明，有必要包括显式水分子以确定稳定的吸附物相，因为（bi）硫酸盐吸附物排通过桥接水分子而变得明显稳定。