Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene
Abstract
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 C1 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 thesemore »
- Authors:
-
[2];
[3];
[4];
[4]
- SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, California 94305, United States, SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States
- SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
- SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, California 94305, United States
- SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- National Energy Research Scientific Computing Center
- OSTI Identifier:
- 1413820
- Alternate Identifier(s):
- OSTI ID: 1420040; OSTI ID: 1508303
- Grant/Contract Number:
- SC0004993; DGE-114747; AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 3 Journal Issue: 12; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kirk, Charlotte, Chen, Leanne D., Siahrostami, Samira, Karamad, Mohammadreza, Bajdich, Michal, Voss, Johannes, Nørskov, Jens K., and Chan, Karen. Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene. United States: N. p., 2017.
Web. doi:10.1021/acscentsci.7b00442.
Kirk, Charlotte, Chen, Leanne D., Siahrostami, Samira, Karamad, Mohammadreza, Bajdich, Michal, Voss, Johannes, Nørskov, Jens K., & Chan, Karen. Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene. United States. https://doi.org/10.1021/acscentsci.7b00442
Kirk, Charlotte, Chen, Leanne D., Siahrostami, Samira, Karamad, Mohammadreza, Bajdich, Michal, Voss, Johannes, Nørskov, Jens K., and Chan, Karen. Mon .
"Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene". United States. https://doi.org/10.1021/acscentsci.7b00442.
@article{osti_1413820,
title = {Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene},
author = {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},
abstractNote = {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 C1 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.},
doi = {10.1021/acscentsci.7b00442},
journal = {ACS Central Science},
number = 12,
volume = 3,
place = {United States},
year = {Mon Dec 18 00:00:00 EST 2017},
month = {Mon Dec 18 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acscentsci.7b00442
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