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Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

Kirk, Charlotte and Chen, Leanne D. and Siahrostami, Samira and Karamad, Mohammadreza and Bajdich, Michal and Voss, Johannes and Nørskov, Jens K. and Chan, Karen (2017) Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene. ACS Central Science, 3 (12). pp. 1286-1293. ISSN 2374-7943. PMCID PMC5746853. doi:10.1021/acscentsci.7b00442.

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Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from CO to be a critical step in C_1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. This work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Chen, Leanne D.0000-0001-9700-972X
Siahrostami, Samira0000-0002-1192-4634
Bajdich, Michal0000-0003-1168-8616
Voss, Johannes0000-0001-7740-8811
Nørskov, Jens K.0000-0002-4427-7728
Chan, Karen0000-0002-6897-1108
Additional Information:© 2017 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: September 25, 2017; Published: December 18, 2017. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. C.K. acknowledges support from the NSF Graduate Research Fellowship program under Grant No. DGE-114747 and from the Morgridge Family Stanford Graduate Fellowship. L.D.C. acknowledges financial support from the Natural Sciences and Engineering Research Council of Canada for the CGS-D3 fellowship. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
NSF Graduate Research FellowshipDGE-114747
Stanford Graduate FellowshipUNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)CGS-D3
Issue or Number:12
PubMed Central ID:PMC5746853
Record Number:CaltechAUTHORS:20171219-112016737
Persistent URL:
Official Citation:Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene. Charlotte Kirk, Leanne D. Chen, Samira Siahrostami, Mohammadreza Karamad, Michal Bajdich, Johannes Voss, Jens K. Nørskov, and Karen Chan. ACS Central Science 2017 3 (12), 1286-1293. DOI: 10.1021/acscentsci.7b00442
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83966
Deposited By: Tony Diaz
Deposited On:19 Dec 2017 19:35
Last Modified:18 Mar 2022 22:17

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