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Title: Cu metal embedded in oxidized matrix catalyst to promote CO 2 activation and CO dimerization for electrochemical reduction of CO 2

We propose and validate with quantum mechanics methods a unique catalyst for electrochemical reduction of CO 2 (CO 2RR) in which selectivity and activity of CO and C 2 products are both enhanced at the borders of oxidized and metallic surface regions. This Cu metal embedded in oxidized matrix (MEOM) catalyst is consistent with observations that Cu 2O-based electrodes improve performance. However, we show that a fully oxidized matrix (FOM) model would not explain the experimentally observed performance boost, and we show that the FOM is not stable under CO2 reduction conditions. This electrostatic tension between the Cu + and Cu0 surface sites responsible for the MEOM mechanism suggests a unique strategy for designing more efficient and selective electrocatalysts for CO 2RR to valuable chemicals (HCO x), a critical need for practical environmental and energy applications.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Grant/Contract Number:
SC0004993
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 26; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1465782

Xiao, Hai, Goddard, William A., Cheng, Tao, and Liu, Yuanyue. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. United States: N. p., Web. doi:10.1073/pnas.1702405114.
Xiao, Hai, Goddard, William A., Cheng, Tao, & Liu, Yuanyue. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. United States. doi:10.1073/pnas.1702405114.
Xiao, Hai, Goddard, William A., Cheng, Tao, and Liu, Yuanyue. 2017. "Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2". United States. doi:10.1073/pnas.1702405114. https://www.osti.gov/servlets/purl/1465782.
@article{osti_1465782,
title = {Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2},
author = {Xiao, Hai and Goddard, William A. and Cheng, Tao and Liu, Yuanyue},
abstractNote = {We propose and validate with quantum mechanics methods a unique catalyst for electrochemical reduction of CO2 (CO2RR) in which selectivity and activity of CO and C2 products are both enhanced at the borders of oxidized and metallic surface regions. This Cu metal embedded in oxidized matrix (MEOM) catalyst is consistent with observations that Cu2O-based electrodes improve performance. However, we show that a fully oxidized matrix (FOM) model would not explain the experimentally observed performance boost, and we show that the FOM is not stable under CO2 reduction conditions. This electrostatic tension between the Cu+ and Cu0 surface sites responsible for the MEOM mechanism suggests a unique strategy for designing more efficient and selective electrocatalysts for CO2RR to valuable chemicals (HCOx), a critical need for practical environmental and energy applications.},
doi = {10.1073/pnas.1702405114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 26,
volume = 114,
place = {United States},
year = {2017},
month = {6}
}

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