Gossenberger Florian, Juarez Fernanda, Groß Axel
Institute of Theoretical Chemistry, Ulm University, Ulm, Germany.
Front Chem. 2020 Jul 31;8:634. doi: 10.3389/fchem.2020.00634. eCollection 2020.
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。采用巨正则方法考虑了电极电位和pH值等电化学控制参数的影响。由此得出了稳定共吸附相作为电化学势函数的相图和Pourbaix图，它们很好地再现了实验结果。我们证明，为了确定稳定的吸附质相，有必要包含显式水分子，因为（亚）硫酸氢根吸附质行通过桥连水分子而显著稳定。
