Insight into CO Activation over Cu(100) under Electrochemical Conditions

Tian Sheng*, Dong Wang, Wen Feng Lin, P. Hu, Shi Gang Sun

*Corresponding author for this work

Research output: Contribution to journalArticle

15 Citations (Scopus)


The reduction of CO2 on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO2 reduction process, the electron transfer to COads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COHads and CHOads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COHads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of CHOads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COHads is more favored than that of CHOads, while CHOads is thermodynamically more stable. This work reveals that CO activation via COHads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO2 electroreduction over Cu electrodes.

Original languageEnglish
Pages (from-to)446-454
Number of pages9
JournalElectrochimica Acta
Early online date07 Jan 2016
Publication statusPublished - 01 Feb 2016


  • ab initio molecular dynamics
  • CO
  • copper electrode
  • density functional theory
  • electroreduction

ASJC Scopus subject areas

  • Electrochemistry
  • Chemical Engineering(all)

Fingerprint Dive into the research topics of 'Insight into CO Activation over Cu(100) under Electrochemical Conditions'. Together they form a unique fingerprint.

  • Cite this