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Published January 11, 2017 | Supplemental Material + Accepted Version
Journal Article Open

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

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.

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.

Attached Files

Accepted Version - jacs_2E6b07557.pdf

Supplemental Material - ja6b07557_si_001.pdf

Supplemental Material - ja6b07557_si_002.pdf

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Additional details

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August 19, 2023
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