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Title: Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

Abstract

Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e or 4e transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H 2O)-mediated mechanism including 4e transfers is identified, where the reduction steps via *H 2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH (aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O 2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding ismore » weak enough to release more surface sites under working conditions, while **O 2 binding is strong enough to enable the ORR via the 4e transfer mechanism.« less

Authors:
 [1];  [2];  [3]
  1. State Univ. of New York (SUNY) at Stony Brook, Stony Brook, NY (United States)
  2. State Univ. of New York (SUNY) at Stony Brook, Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1328388
Report Number(s):
BNL-112715-2016-JA
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0301020
Grant/Contract Number:  
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 28; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
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. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b05126.
Liu, Shizhong, White, Michael G., & Liu, Ping. Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface. United States. https://doi.org/10.1021/acs.jpcc.6b05126
Liu, Shizhong, White, Michael G., and Liu, Ping. Thu . "Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface". United States. https://doi.org/10.1021/acs.jpcc.6b05126. https://www.osti.gov/servlets/purl/1328388.
@article{osti_1328388,
title = {Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface},
author = {Liu, Shizhong and White, Michael G. and Liu, Ping},
abstractNote = {Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e– or 4e– transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H2O)-mediated mechanism including 4e– transfers is identified, where the reduction steps via *H2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH–(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O2 binding is strong enough to enable the ORR via the 4e– transfer mechanism.},
doi = {10.1021/acs.jpcc.6b05126},
url = {https://www.osti.gov/biblio/1328388}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 28,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}

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