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The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons

Velasco-Vélez, J-J; Jones, TE; Gao, D; Carbonio, E; Arrigo, R; Hsu, C-J; Huang, Y-C; Dong, CL; Chen, J-M; Lee, J-F; Strasser, P; Roldan-Cuenya, B; Schloegl, R; Knop-Gericke, A; Chuang, C

The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons Thumbnail


Authors

J-J Velasco-Vélez

TE Jones

D Gao

E Carbonio

C-J Hsu

Y-C Huang

CL Dong

J-M Chen

J-F Lee

P Strasser

B Roldan-Cuenya

R Schloegl

A Knop-Gericke

C Chuang



Abstract

Redox-active copper catalysts with accurately prepared oxidation states (Cu0, Cu+ and Cu2+) and high selectivity to C2 hydrocarbon formation, from electrocatalytic cathodic reduction of CO2, were fabricated and characterized. The electrochemically prepared copper-redox electro-cathodes yield higher activity for the production of hydrocarbons at lower oxidation state. By combining advanced X-ray spectroscopy and in situ micro-reactors it was possible to unambiguously reveal the variation in the complex electronic structure that the catalysts undergo at different stages (i.e. during fabrication and electrocatalytic reactions). It was found that the surface, sub-surface and bulk properties of the electrochemically prepared catalysts are dominated by the formation of copper carbonates on the surface of cupric-like oxides, which prompts catalyst deactivation by restraining effective charge transport. Furthermore, the formation of reduced or partially-reduced copper catalysts yields the key dissociative proton-consuming reactive adsorption of CO2 to produce CO, allowing the subsequent hydrogenation into C2 and C1 products by dimerization and protonation. These results yield valuable information on the variations in the electronic structure that redox-active copper catalysts undergo in the course of the electrochemical reaction, which, under extreme conditions are mediated by thermodynamics but, critically, kinetics dominate near the oxide/metal phase transitions.

Citation

Velasco-Vélez, J., Jones, T., Gao, D., Carbonio, E., Arrigo, R., Hsu, C., …Chuang, C. (2018). The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons. ACS sustainable chemistry & engineering, 7(1), 1485-1492. https://doi.org/10.1021/acssuschemeng.8b05106

Journal Article Type Article
Acceptance Date Nov 1, 2018
Online Publication Date Nov 29, 2018
Publication Date Nov 29, 2018
Deposit Date Dec 4, 2018
Publicly Available Date Nov 29, 2019
Journal ACS Sustainable Chemistry & Engineering
Electronic ISSN 2168-0485
Publisher American Chemical Society
Volume 7
Issue 1
Pages 1485-1492
DOI https://doi.org/10.1021/acssuschemeng.8b05106
Publisher URL https://doi.org/10.1021/acssuschemeng.8b05106

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CO2RR on EC prepared CuOx Oxides_SusChemEng_SI_Final Suppl.pdf (665 Kb)
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CO2RR on EC prepared CuOx Oxides_ACS SusChemEng_Final.pdf (889 Kb)
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