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

He, Haiying; Morrissey, Christopher; Curtiss, Larry A.; Zapol, Peter

doi:10.1021/acs.jpcc.8b07887

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

Journal Article · Mon Nov 26 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b07887· OSTI ID:1490428

He, Haiying ^[1]; Morrissey, Christopher ^[1]; ^[2]; ^[2]

Valparaiso Univ., IN (United States). Dept. of Physics and Astronomy
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1490428

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 50 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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