Accepted PCCP paper c6cp02198k.pdf (1.64 MB)

Electrochemical interfacial influences on deoxygenation and hydrogenation reactions in CO reduction on a Cu(100) surface.

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journal contribution
posted on 02.06.2016, 13:04 by Tian Sheng, Wen-Feng Lin, Shi-Gang Sun
Electroreduction of CO2 to hydrocarbons on a copper surface has attracted much attention in the last few decades for providing a sustainable way for energy storage. During the CO2 and further CO electroreduction processes, deoxygenation that is C-O bond dissociation, and hydrogenation that is C-H bond formation, are two main types of surface reactions catalyzed by the copper electrode. In this work, by performing the state-of-the-art constrained ab initio molecular dynamics simulations, we have systematically investigated deoxygenation and hydrogenation reactions involving two important intermediates, COHads and CHOads, under various conditions of (i) on a Cu(100) surface without water molecules, (ii) at the water/Cu(100) interface and (iii) at the charged water/Cu(100) interface, in order to elucidate the electrochemical interfacial influences. It has been found that the electrochemical interface can facilitate considerably the C-O bond dissociation via changing the reaction mechanisms. However, C-H bond formation has not been affected by the presence of water or electrical charge. Furthermore, the promotional roles of an aqueous environment and negative electrode potential in deoxygenation have been clarified, respectively. This fundamental study provides an atomic level insight into the significance of the electrochemical interface towards electrocatalysis, which is of general importance for understanding electrochemistry.

Funding

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

History

School

  • Aeronautical, Automotive, Chemical and Materials Engineering

Department

  • Chemical Engineering

Published in

Physical chemistry chemical physics : PCCP

Citation

SHENG, T., LIN, W-F. and SUN, S-G., 2016. Electrochemical interfacial influences on deoxygenation and hydrogenation reactions in CO reduction on a Cu(100) surface. Physical Chemistry Chemical Physics, 18, pp. 15304-15311.

Publisher

© The Authors. Published by the Royal Soicety of Chemistry

Version

AM (Accepted Manuscript)

Publisher statement

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/

Publication date

2016

Notes

This paper was accepted for publication in the journal Physical Chemistry Chemical Physics and the definitive published version is available at http://dx.doi.org/10.1039/C6CP02198K.

ISSN

1463-9076

eISSN

1463-9084

Language

en

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