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Title: Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study

Abstract

We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e- or 4 e- mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e- network including both a chemisorbed water (*H2O)-mediated 4 e- associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. On the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O2 reduction by *H2O, and suppressing **O2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.

Authors:
 [1];  [2]; ORCiD logo [3]
  1. State Univ. of New York (SUNY), Stony Brook, NY (United States). Chemistry Dept.
  2. State Univ. of New York (SUNY), Stony Brook, NY (United States). Chemistry Dept.; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1424995
Alternate Identifier(s):
OSTI ID: 1418069
Report Number(s):
BNL-114833-2017-JAAM
Journal ID: ISSN 1867-3880
Grant/Contract Number:  
SC0012704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Shizhong, White, Michael G., and Liu, Ping. Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study. United States: N. p., 2018. Web. doi:10.1002/cctc.201701539.
Liu, Shizhong, White, Michael G., & Liu, Ping. Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study. United States. doi:10.1002/cctc.201701539.
Liu, Shizhong, White, Michael G., and Liu, Ping. Thu . "Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study". United States. doi:10.1002/cctc.201701539. https://www.osti.gov/servlets/purl/1424995.
@article{osti_1424995,
title = {Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study},
author = {Liu, Shizhong and White, Michael G. and Liu, Ping},
abstractNote = {We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e- or 4 e- mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e- network including both a chemisorbed water (*H2O)-mediated 4 e- associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. On the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O2 reduction by *H2O, and suppressing **O2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.},
doi = {10.1002/cctc.201701539},
journal = {ChemCatChem},
number = 3,
volume = 10,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: Optimized structures for a single water bilayer adsorbed on Ag(111)in both (a) H-up top and side views (b) H-down top and side views (Grey, Ag; red, O; white, H).

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