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The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO_2 (110) Surface

Ping, Yuan and Nielsen, Robert J. and Goddard, William A. (2017) The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO_2 (110) Surface. Journal of the American Chemical Society, 139 (1). pp. 149-155. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20161213-102614547

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Abstract

How to efficiently oxidize H_2O to O_2 (Oxygen Evolution Reaction –OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO_2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work we performed first principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OER at the IrO_2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the micro-kinetic models. This allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b07557DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b07557PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b07557PublisherSupporting Information
ORCID:
AuthorORCID
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A.0000-0003-0097-5716
Alternate Title:The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO2 (110) Surface
Additional Information:© 2016 American Chemical Society. Received: July 21, 2016; Published: December 9, 2016. We thank Dr. Ravishankar Sundararaman, Dr. Hai Xiao, Dr. Tao Cheng, and Dr. Yan Choi Lam for useful discussions. This paper is based on work performed in Joint Center for artificial photosynthesis—a DOE innovation hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1246
Issue or Number:1
Record Number:CaltechAUTHORS:20161213-102614547
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20161213-102614547
Official Citation:The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO2 (110) Surface Yuan Ping, Robert J. Nielsen, and William A. Goddard III Journal of the American Chemical Society 2017 139 (1), 149-155 DOI: 10.1021/jacs.6b07557
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:72768
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:13 Dec 2016 18:57
Last Modified:21 Feb 2020 17:12

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