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Title: Investigating the Role of Copper Oxide in Electrochemical CO 2 Reduction in Real Time

Abstract

Copper oxides have been of considerable interest as electrocatalysts for CO2 reduction (CO2R) in aqueous electrolytes. However, their role as an active catalyst in reducing the required overpotential and improving the selectivity of reaction compared with that of polycrystalline copper remains controversial. Here, we introduce the use of selected-ion flow tube mass spectrometry, in concert with chronopotentiometry, in situ Raman spectroscopy, and computational modeling, to investigate CO2R on Cu2O nanoneedles, Cu2O nanocrystals, and Cu2O nanoparticles. We show experimentally that the selective formation of gaseous C2 products (i.e., ethylene) in CO2R is preceded by the reduction of the copper oxide (Cu2OR) surface to metallic copper. On the basis of density functional theory modeling, CO2R products are not formed as long as Cu2O is present at the surface because Cu2OR is kinetically and energetically more favorable than CO2R.

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [3];  [4]; ORCiD logo [5];  [4]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [6];  [7]
  1. A Singapore Berkeley Research Initiative for Sustainable Energy, Berkeley Educational Alliance for Research in Singapore, 1 CREATE Way, 138602 Singapore; NUSNNI-Nanocore, National University of Singapore, 117411 Singapore
  2. Yale Energy Sciences Institute and Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, United States
  3. A Singapore Berkeley Research Initiative for Sustainable Energy, Berkeley Educational Alliance for Research in Singapore, 1 CREATE Way, 138602 Singapore; Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, 117543 Singapore
  4. A Singapore Berkeley Research Initiative for Sustainable Energy, Berkeley Educational Alliance for Research in Singapore, 1 CREATE Way, 138602 Singapore
  5. NUSNNI-Nanocore, National University of Singapore, 117411 Singapore
  6. A Singapore Berkeley Research Initiative for Sustainable Energy, Berkeley Educational Alliance for Research in Singapore, 1 CREATE Way, 138602 Singapore; Department of Physics, National University of Singapore, 117542 Singapore; Centre for Advanced 2D Materials, National University of Singapore, 6 Science Drive 2, 117546 Singapore
  7. A Singapore Berkeley Research Initiative for Sustainable Energy, Berkeley Educational Alliance for Research in Singapore, 1 CREATE Way, 138602 Singapore; NUSNNI-Nanocore, National University of Singapore, 117411 Singapore; Department of Physics, National University of Singapore, 117542 Singapore; Department of Electrical and Computer Engineering, National University of Singapore, 117576 Singapore; Department of Integrative Science and Engineering, National University of Singapore, 117456 Singapore
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1485128
Resource Type:
Journal Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 10; Journal ID: ISSN 1944-8244
Country of Publication:
United States
Language:
English

Citation Formats

Mandal, Lily, Yang, Ke R., Motapothula, Mallikarjuna Rao, Ren, Dan, Lobaccaro, Peter, Patra, Abhijeet, Sherburne, Matthew, Batista, Victor S., Yeo, Boon Siang, Ager, Joel W., Martin, Jens, and Venkatesan, T. Investigating the Role of Copper Oxide in Electrochemical CO 2 Reduction in Real Time. United States: N. p., 2018. Web. doi:10.1021/acsami.7b15418.
Mandal, Lily, Yang, Ke R., Motapothula, Mallikarjuna Rao, Ren, Dan, Lobaccaro, Peter, Patra, Abhijeet, Sherburne, Matthew, Batista, Victor S., Yeo, Boon Siang, Ager, Joel W., Martin, Jens, & Venkatesan, T. Investigating the Role of Copper Oxide in Electrochemical CO 2 Reduction in Real Time. United States. doi:10.1021/acsami.7b15418.
Mandal, Lily, Yang, Ke R., Motapothula, Mallikarjuna Rao, Ren, Dan, Lobaccaro, Peter, Patra, Abhijeet, Sherburne, Matthew, Batista, Victor S., Yeo, Boon Siang, Ager, Joel W., Martin, Jens, and Venkatesan, T. Tue . "Investigating the Role of Copper Oxide in Electrochemical CO 2 Reduction in Real Time". United States. doi:10.1021/acsami.7b15418.
@article{osti_1485128,
title = {Investigating the Role of Copper Oxide in Electrochemical CO 2 Reduction in Real Time},
author = {Mandal, Lily and Yang, Ke R. and Motapothula, Mallikarjuna Rao and Ren, Dan and Lobaccaro, Peter and Patra, Abhijeet and Sherburne, Matthew and Batista, Victor S. and Yeo, Boon Siang and Ager, Joel W. and Martin, Jens and Venkatesan, T.},
abstractNote = {Copper oxides have been of considerable interest as electrocatalysts for CO2 reduction (CO2R) in aqueous electrolytes. However, their role as an active catalyst in reducing the required overpotential and improving the selectivity of reaction compared with that of polycrystalline copper remains controversial. Here, we introduce the use of selected-ion flow tube mass spectrometry, in concert with chronopotentiometry, in situ Raman spectroscopy, and computational modeling, to investigate CO2R on Cu2O nanoneedles, Cu2O nanocrystals, and Cu2O nanoparticles. We show experimentally that the selective formation of gaseous C2 products (i.e., ethylene) in CO2R is preceded by the reduction of the copper oxide (Cu2OR) surface to metallic copper. On the basis of density functional theory modeling, CO2R products are not formed as long as Cu2O is present at the surface because Cu2OR is kinetically and energetically more favorable than CO2R.},
doi = {10.1021/acsami.7b15418},
journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 10,
volume = 10,
place = {United States},
year = {2018},
month = {2}
}