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Title: Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction

Abstract

Bimetallic catalysts are attractive alternatives to extend the parameter space that can be tuned for support interactions and catalytic performance. In this study, we have investigated the smallest bimetallic catalysts dimers supported on defective graphene for the electrochemical reduction of CO 2 to CH 4 based on a first-principles approach and the computational hydrogen electrode model. The monometallic and bimetallic dimers formed from Group 10 (Ni, Pd, Pt) and group 11 (Cu, Ag, Au) elements are characterized by a positively charged anchoring atom occupying the vacancy site of graphene and a neutral or slightly negatively charged antenna atom sticking out from the graphene surface. The strong selective binding of these dimers ensures their high stability. Possible rate-limiting steps are identified from the full reaction pathways to generate CH4. Overall, Pt-2, AgNi, Pd-2, and AgPt are the best candidates with the lowest overpotential values of 0.37, 0.69, 0.69, and 0.76 V, respectively. It is found that the alloy effect and the interaction with support help to optimize the property. These metallic dimers, however, retain nonmonotonous property relationships that give opportunity to go beyond scaling behavior and look for a few atom catalysts that have unique properties to reduce rate-limiting potentials andmore » improve the catalytic performance.« less

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Valparaiso Univ., IN (United States). Dept. of Physics and Astronomy
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1490428
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 50; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

He, Haiying, Morrissey, Christopher, Curtiss, Larry A., and Zapol, Peter. Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b07887.
He, Haiying, Morrissey, Christopher, Curtiss, Larry A., & Zapol, Peter. Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction. United States. doi:10.1021/acs.jpcc.8b07887.
He, Haiying, Morrissey, Christopher, Curtiss, Larry A., and Zapol, Peter. Mon . "Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction". United States. doi:10.1021/acs.jpcc.8b07887. https://www.osti.gov/servlets/purl/1490428.
@article{osti_1490428,
title = {Graphene-Supported Monometallic and Bimetallic Dimers for Electrochemical CO 2 Reduction},
author = {He, Haiying and Morrissey, Christopher and Curtiss, Larry A. and Zapol, Peter},
abstractNote = {Bimetallic catalysts are attractive alternatives to extend the parameter space that can be tuned for support interactions and catalytic performance. In this study, we have investigated the smallest bimetallic catalysts dimers supported on defective graphene for the electrochemical reduction of CO2 to CH4 based on a first-principles approach and the computational hydrogen electrode model. The monometallic and bimetallic dimers formed from Group 10 (Ni, Pd, Pt) and group 11 (Cu, Ag, Au) elements are characterized by a positively charged anchoring atom occupying the vacancy site of graphene and a neutral or slightly negatively charged antenna atom sticking out from the graphene surface. The strong selective binding of these dimers ensures their high stability. Possible rate-limiting steps are identified from the full reaction pathways to generate CH4. Overall, Pt-2, AgNi, Pd-2, and AgPt are the best candidates with the lowest overpotential values of 0.37, 0.69, 0.69, and 0.76 V, respectively. It is found that the alloy effect and the interaction with support help to optimize the property. These metallic dimers, however, retain nonmonotonous property relationships that give opportunity to go beyond scaling behavior and look for a few atom catalysts that have unique properties to reduce rate-limiting potentials and improve the catalytic performance.},
doi = {10.1021/acs.jpcc.8b07887},
journal = {Journal of Physical Chemistry. C},
number = 50,
volume = 122,
place = {United States},
year = {2018},
month = {11}
}

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