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Title: Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling

Abstract

Abstract Oxide‐derived (OD) Cu catalysts have high selectivity towards the formation of multi‐carbon products (C 2 /C 3 ) for aqueous electrochemical CO 2 reduction (CO 2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O‐enriched OD Cu catalysts and testing them for CO 2 R. These catalysts maintain a high selectivity towards C 2 /C 3 products (ca. 60 %) for up to 5 h in 0.1  m KHCO 3 at −1.0 V vs. RHE. However, secondary‐ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO 2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation Singapore
OSTI Identifier:
1530326
Alternate Identifier(s):
OSTI ID: 1412581
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 2; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; copper oxides; electrocatalysis; isotope labeling; oxide stability

Citation Formats

Lum, Yanwei, and Ager, Joel W. Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling. United States: N. p., 2017. Web. doi:10.1002/anie.201710590.
Lum, Yanwei, & Ager, Joel W. Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling. United States. https://doi.org/10.1002/anie.201710590
Lum, Yanwei, and Ager, Joel W. Tue . "Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling". United States. https://doi.org/10.1002/anie.201710590. https://www.osti.gov/servlets/purl/1530326.
@article{osti_1530326,
title = {Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction Investigated with 18O Labeling},
author = {Lum, Yanwei and Ager, Joel W.},
abstractNote = {Abstract Oxide‐derived (OD) Cu catalysts have high selectivity towards the formation of multi‐carbon products (C 2 /C 3 ) for aqueous electrochemical CO 2 reduction (CO 2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O‐enriched OD Cu catalysts and testing them for CO 2 R. These catalysts maintain a high selectivity towards C 2 /C 3 products (ca. 60 %) for up to 5 h in 0.1  m KHCO 3 at −1.0 V vs. RHE. However, secondary‐ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO 2 R. Furthermore, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content.},
doi = {10.1002/anie.201710590},
journal = {Angewandte Chemie (International Edition)},
number = 2,
volume = 57,
place = {United States},
year = {Tue Nov 07 00:00:00 EST 2017},
month = {Tue Nov 07 00:00:00 EST 2017}
}

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Cited by: 261 works
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Figures / Tables:

Figure 1 Figure 1: (a) Electrochemical oxidation and reduction procedure for generating OD18 Cu. The blue box highlights the oxidation stage and the green box highlights the reduction stage. SEM images are shown as insets (scale bars: 0.5 µm) (b) Faradaic efficiency to C2/C3, C1 and hydrogen for OD Cu, Cu filmmore » and Cu foil (70 min tests). Average current densities are given in parenthesis (full data in Tables S2 to S5). (c) 5 h long CO2R with OD18 Cu. Graph shows current density (black line) and faradaic efficiency to ethylene (red squares) vs time. See Figure S9 for faradaic efficiency to other gas products. Error bars are standard deviations from 3 repeat experiments.« less

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