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

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. As a result, this work highlightsmore » the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [3] ;  [4] ; ORCiD logo [4] ;  [1] ; ORCiD logo [4]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. Stanford Univ., Stanford, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
SC0004993; DGE-114747; AC02-76SF00515
Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 12; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1413820
Alternate Identifier(s):
OSTI ID: 1420040