A Cation Concentration Gradient Approach to Tune the Selectivity and Activity of CO2 Electroreduction

Wenhao Ren*, Aoni Xu, Karen Chan, Xile Hu*

*Corresponding author for this work

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The linear scaling relationship of the binding energies of different intermediates limits the catalyst performance in CO2 electroreduction. Here we demonstrate a cation concentration gradient strategy to promote the activity and tune the selectivity of CO2 electroreduction, thereby breaking the scaling relationship. In optimal concentrations of the potassium acetate (KAc) electrolyte, Cu, Ag and In catalysts deliver current densities that are 7.1, 3.2, 2.7 times higher than those obtained in 0.5 M KAc for C2H4, CO, and formate production, respectively. Increasing the concentration of KAc also changes the selectivity from CO to formate on Ag, and from CO to C2 products on Cu. In situ surface-enhanced Raman spectroscopy and computational simulations reveal that the binding energies of intermediates are changed at different electrolyte concentrations, which is due to a local electrostatic interaction modulated by potassium cations at the electrode surface.

Original languageEnglish
Article numbere202214173
JournalAngewandte Chemie - International Edition
Issue number49
Number of pages7
Publication statusPublished - 2022


  • CO2Reduction
  • Cation Effect
  • Concentration Gradient
  • Electrocatalysis


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