English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Revealing the CO Coverage Driven C-C Coupling Mechanism for Electrochemical CO2 Reduction on Cu2O Nanocubes via Operando Raman Spectroscopy

MPS-Authors
/persons/resource/persons262448

Zhan,  Chao
Interface Science, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons227610

Rettenmaier,  Clara
Interface Science, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons214068

Bergmann,  Arno
Interface Science, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21771

Kühl,  Stefanie
Interface Science, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons22020

Roldan Cuenya,  Beatriz
Interface Science, Fritz Haber Institute, Max Planck Society;

External Resource
No external resources are shared
Fulltext (public)

acscatal.1c01478.pdf
(Publisher version), 4MB

Supplementary Material (public)
There is no public supplementary material available
Citation

Zhan, C., Dattila, F., Rettenmaier, C., Bergmann, A., Kühl, S., García-Muelas, R., et al. (2021). Revealing the CO Coverage Driven C-C Coupling Mechanism for Electrochemical CO2 Reduction on Cu2O Nanocubes via Operando Raman Spectroscopy. ACS Catalysis, 11, 7694-7701. doi:10.1021/acscatal.1c01478.


Cite as: http://hdl.handle.net/21.11116/0000-0008-9F8D-7
Abstract
Electrochemical reduction of carbon dioxide (CO2RR) is an attractive route to close the carbon cycle and potentially turn CO2 into valuable chemicals and fuels. However, the highly selective generation of multicarbon products remains a challenge, suffering from poor mechanistic understanding. Herein, we used operando Raman spectroscopy to track the potential-dependent reduction of Cu2O nanocubes and the surface coverage of reaction intermediates. In particular, we discovered that the potential-dependent intensity ratio of the Cu–CO stretching band to the CO rotation band follows a volcano trend similar to the CO2RR Faradaic efficiency for multicarbon products. By combining operando spectroscopic insights with Density Functional Theory, we proved that this ratio is determined by the CO coverage and that a direct correlation exists between the potential-dependent CO coverage, the preferred C–C coupling configuration, and the selectivity to C2+ products. Thus, operando Raman spectroscopy can serve as an effective method to quantify the coverage of surface intermediates during an electrocatalytic reaction.