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Cu metal embedded in oxidized matrix catalyst to promote CO_2 activation and CO dimerization for electrochemical reduction of CO_2

Xiao, Hai and Goddard, William A. and Cheng, Tao and Liu, Yuanyue (2017) Cu metal embedded in oxidized matrix catalyst to promote CO_2 activation and CO dimerization for electrochemical reduction of CO_2. Proceedings of the National Academy of Sciences of the United States of America, 114 (26). pp. 6685-6688. ISSN 0027-8424. PMCID PMC5495255.

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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 CO_2 reduction conditions. This electrostatic tension between the Cu^+ and Cu^0 surface sites responsible for the MEOM mechanism suggests a unique strategy for designing more efficient and selective electrocatalysts for CO_2RR to valuable chemicals (HCOx), a critical need for practical environmental and energy applications.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Xiao, Hai0000-0001-9399-1584
Goddard, William A.0000-0003-0097-5716
Cheng, Tao0000-0003-4830-177X
Liu, Yuanyue0000-0002-5880-8649
Additional Information:© 2017 National Academy of Sciences. Freely available online through the PNAS open access option. Contributed by William A. Goddard III, May 9, 2017 (sent for review February 13, 2017; reviewed by Timo Jacob and Bruce Parkinson). This research was supported by the Joint Center for Artificial Photosynthesis, a Department of Energy (DOE) Energy Innovation Hub, supported through the Office of Science of the US DOE under Award DE-SC0004993. This work used the computational resources of Zwicky (at California Institute of Technology). Author contributions: H.X. and W.A.G. designed research; H.X. and T.C. performed research; H.X., W.A.G., T.C., and Y.L. analyzed data; and H.X. and W.A.G. wrote the paper. Reviewers: T.J., Universität Ulm; and B.P., University of Wyoming. The authors declare no conflict of interest. This article contains supporting information online at
Group:JCAP, Resnick Sustainability Institute
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Subject Keywords:electrochemical reduction of CO_2; Cu metal embedded in oxidized matrix; density functional theory; CO_2 activation; CO dimerization
Issue or Number:26
PubMed Central ID:PMC5495255
Record Number:CaltechAUTHORS:20170613-083147382
Persistent URL:
Official Citation:Hai Xiao, William A. Goddard III, Tao Cheng, and Yuanyue Liu Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2 PNAS 2017 114 (26) 6685-6688; published ahead of print June 12, 2017, doi:10.1073/pnas.1702405114
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78146
Deposited By: Donna Wrublewski
Deposited On:13 Jun 2017 16:13
Last Modified:03 Oct 2019 18:05

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