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Electrolyte concentration modulates the surface structure evolution of Au(111) cathodes.

Yue Feng1,2, Yu-Qi Wang1, Jiaju Fu1

  • 1CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 China wyqchem@iccas.ac.cn wangd@iccas.ac.cn wanlijun@iccas.ac.cn.

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|January 19, 2026
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Summary

Electrolyte concentration dictates gold surface changes during electrocatalysis. Lowering alkali metal cation concentration drives surface roughening, enhancing carbon dioxide reduction reaction performance.

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Area of Science:

  • Surface Science
  • Electrocatalysis
  • Materials Chemistry

Background:

  • Understanding electrode surface structure is key to electrocatalysis.
  • Electrolyte composition significantly influences interfacial reactions.

Purpose of the Study:

  • To investigate how alkali metal cation concentration affects Au(111) surface structure under cathodic polarization.
  • To correlate in situ surface morphology changes with carbon dioxide reduction reaction (CO2RR) performance.

Main Methods:

  • In situ electrochemical scanning tunneling microscopy (EC-STM) was used to visualize surface structure evolution.
  • Electrochemical measurements were performed to assess CO2RR activity.

Main Results:

  • Decreasing alkali metal cation concentration ([AM+]) from 1 M to 0.2 M induced surface roughening, progressing from corrosion to pit and nanocluster formation, and finally to pit-free nanoclusters via atomic migration.
  • Surface modifications amplified these structural changes at lower [AM+].
  • Increased surface roughness correlated with enhanced CO2RR performance.

Conclusions:

  • Alkali metal cations play a critical role in regulating electrochemical interfaces and in situ surface structures.
  • Electrolyte concentration is a key factor in tuning electrode surface morphology for improved electrocatalytic activity, particularly for CO2RR.