Loughborough University
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Insight into CO activation over Cu(100) under electrochemical conditions

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journal contribution
posted on 2016-02-10, 13:33 authored by Tian Sheng, Dong Wang, Wen-Feng LinWen-Feng Lin, Peijun Hu, Shi-Gang Sun
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.


Financial supports from the NSFC (21361140374, 21321062, 21333003 and 21573183) are acknowledged.



  • Aeronautical, Automotive, Chemical and Materials Engineering


  • Chemical Engineering

Published in

Electrochimica Acta




446 - 454


SHENG, T. ... et al., 2016. Insight into CO Activation over Cu(100) under Electrochemical Conditions. Electrochimica Acta, 190, pp.446-454.


Crown Copyright © Published by Elsevier Ltd.


  • AM (Accepted Manuscript)

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This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

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This paper was accepted for publication in the journal Electrochimica Acta and the definitive published version is available at http://dx.doi.org/10.1016/j.electacta.2016.01.037.




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