期刊
CHEMICAL COMMUNICATIONS
卷 56, 期 3, 页码 427-430出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9cc07769c
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资金
- V-Sustain: the VILLUM Centre for the Science of Sustainable Fuels and Chemicals from VILLUM FONDEN [9455]
Electrochemical reaction rates are sensitive to interactions between electrolyte cations and adsorbed reaction intermediates, e.g., cation-*OH interactions in the oxygen reduction reaction on platinum. Here, we calculate the free energy interaction between adsorbed *OH and K+/Li+ situated at the liquid water-Pt(111) interface using ab initio molecular dynamics (AIMD) and metadynamics. Li+ stabilizes *OH by 0.1 +/- 0.1 eV and K+ destabilizes *OH by 0.1 +/- 0.1 eV, in qualitative agreement with experimental cyclic voltammogram (CV) measurements. In contrast, the internal energy of *OH is stabilized by 0.3 eV and 0.4 eV for Li+ and K+, respectively. This demonstrates that entropy significantly destabilizes cation-*OH interactions and is vital in order to understand even the relative influence of cations at interfaces.
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