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Title: Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction

Abstract

In this study, we have investigated a hierarchical CuO-derived inverse opal (CuO-IO) catalyst with high CO selectivity up to 80–90% and minimal H 2 evolution at moderate potentials for CO 2 electroreduction. The three-dimensionally (3D) structured, porous catalyst was composed of small CuO nanoparticles and exhibited a peak CO faradaic efficiency (FE) of 72.5% (±1.8), complete suppression of H 2 formation, and good stability over 24 hours operation at –0.6 V versus the reversible hydrogen electrode (RHE). In situ Raman, X-ray absorption spectroscopy and X-ray diffraction measurements indicated reduction of the catalyst into metallic Cu0 oxidation state with dominant Cu(111) orientation under electrocatalytic conditions. We suggest that rapid depletion of CO 2 and protons at the highly roughened catalyst surface likely increased the local pH during the electrolysis. The combination of C 1 favoring Cu(111) surfaces and reduced local proton/CO 2 availability facilitated selective conversion of CO 2 into CO and reduced H 2 and C 2 products. Our work provides additional understanding of the structure–property relationships of 3D porous electrocatalysts for CO 2 reduction applications by evaluating the crystallographic orientation, oxidation state, and crystallite size of a CO-selective CuO-IO catalyst under realistic working conditions.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3];  [2];  [2];  [4];  [2];  [1]; ORCiD logo [3];  [2]; ORCiD logo [2]
  1. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); Leidos Research Support Team, Pittsburgh, PA (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1583111
Alternate Identifier(s):
OSTI ID: 1576679
Report Number(s):
BNL-213530-2020-JAAM
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 7; Journal Issue: 48; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Nguyen-Phan, Thuy-Duong, Wang, Congjun, Marin, Chris M., Zhou, Yunyun, Stavitski, Eli, Popczun, Eric J., Yu, Yang, Xu, Wenqian, Howard, Bret H., Stuckman, Mengling Y., Waluyo, Iradwikanari, Ohodnicki, Jr., Paul R., and Kauffman, Douglas R. Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction. United States: N. p., 2019. Web. doi:10.1039/C9TA10135G.
Nguyen-Phan, Thuy-Duong, Wang, Congjun, Marin, Chris M., Zhou, Yunyun, Stavitski, Eli, Popczun, Eric J., Yu, Yang, Xu, Wenqian, Howard, Bret H., Stuckman, Mengling Y., Waluyo, Iradwikanari, Ohodnicki, Jr., Paul R., & Kauffman, Douglas R. Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction. United States. doi:10.1039/C9TA10135G.
Nguyen-Phan, Thuy-Duong, Wang, Congjun, Marin, Chris M., Zhou, Yunyun, Stavitski, Eli, Popczun, Eric J., Yu, Yang, Xu, Wenqian, Howard, Bret H., Stuckman, Mengling Y., Waluyo, Iradwikanari, Ohodnicki, Jr., Paul R., and Kauffman, Douglas R. Tue . "Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction". United States. doi:10.1039/C9TA10135G.
@article{osti_1583111,
title = {Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction},
author = {Nguyen-Phan, Thuy-Duong and Wang, Congjun and Marin, Chris M. and Zhou, Yunyun and Stavitski, Eli and Popczun, Eric J. and Yu, Yang and Xu, Wenqian and Howard, Bret H. and Stuckman, Mengling Y. and Waluyo, Iradwikanari and Ohodnicki, Jr., Paul R. and Kauffman, Douglas R.},
abstractNote = {In this study, we have investigated a hierarchical CuO-derived inverse opal (CuO-IO) catalyst with high CO selectivity up to 80–90% and minimal H2 evolution at moderate potentials for CO2 electroreduction. The three-dimensionally (3D) structured, porous catalyst was composed of small CuO nanoparticles and exhibited a peak CO faradaic efficiency (FE) of 72.5% (±1.8), complete suppression of H2 formation, and good stability over 24 hours operation at –0.6 V versus the reversible hydrogen electrode (RHE). In situ Raman, X-ray absorption spectroscopy and X-ray diffraction measurements indicated reduction of the catalyst into metallic Cu0 oxidation state with dominant Cu(111) orientation under electrocatalytic conditions. We suggest that rapid depletion of CO2 and protons at the highly roughened catalyst surface likely increased the local pH during the electrolysis. The combination of C1 favoring Cu(111) surfaces and reduced local proton/CO2 availability facilitated selective conversion of CO2 into CO and reduced H2 and C2 products. Our work provides additional understanding of the structure–property relationships of 3D porous electrocatalysts for CO2 reduction applications by evaluating the crystallographic orientation, oxidation state, and crystallite size of a CO-selective CuO-IO catalyst under realistic working conditions.},
doi = {10.1039/C9TA10135G},
journal = {Journal of Materials Chemistry. A},
number = 48,
volume = 7,
place = {United States},
year = {2019},
month = {11}
}

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