The microstructural features and charge–potential relation of an electric double layer (EDL) at a stepped Pt(553)/water interface are investigated using ab initio molecular dynamics simulation. The results indicate that the chemisorbed O-down water molecules gather at the (110) step sites, while the (111) terrace sites are covered by the H-down water molecules, which greatly weakens the push-back effect of interface water on the spillover electrons of the stepped surface and, therefore, results in a much more positive potential of zero charge (PZC) than the extended low-index Pt surfaces. It is further revealed that around the PZC, the change in the surface charge density is dominated by the change in the coverage of chemisorbed water molecules, while EDL charging is the main cause of the change in the surface charge density at potential away from the PZC, thus leading to an S-shaped charge–potential relation and a maximum interface capacitance around PZC. Our results make up for the current lack of the atomic-scale understanding of the EDL microstructures and charge–potential relation on the real electrode surfaces with plentiful step and defect sites.
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14 March 2022
Research Article|
March 08 2022
Microscopic EDL structures and charge–potential relation on stepped platinum surface: Insights from the ab initio molecular dynamics simulations
Special Collection:
The Chemical Physics of the Electrode-Electrolyte Interface
Peng Li
;
Peng Li
College of Chemistry and Molecular Sciences, Wuhan University
, Wuhan 430072, China
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Yuwen Liu;
Yuwen Liu
College of Chemistry and Molecular Sciences, Wuhan University
, Wuhan 430072, China
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Shengli Chen
Shengli Chen
a)
College of Chemistry and Molecular Sciences, Wuhan University
, Wuhan 430072, China
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on The Chemical Physics of the Electrode–Electrolyte Interface.
J. Chem. Phys. 156, 104701 (2022)
Article history
Received:
November 29 2021
Accepted:
February 16 2022
Citation
Peng Li, Yuwen Liu, Shengli Chen; Microscopic EDL structures and charge–potential relation on stepped platinum surface: Insights from the ab initio molecular dynamics simulations. J. Chem. Phys. 14 March 2022; 156 (10): 104701. https://doi.org/10.1063/5.0080104
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