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Title: Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction

Abstract

The oxygen evolution reaction (OER) is critical to solar production of fuels, but the reaction mechanism underlying the performance for a best OER catalyst, Fe-doped NiOOH [(Ni,Fe)OOH], remains highly controversial. We used grand canonical quantum mechanics to predict the OER mechanisms including kinetics and thus overpotentials as a function of Fe content in (Ni,Fe)OOH catalysts. We find that density functional theory (DFT) without exact exchange predicts that addition of Fe does not reduce the overpotential much. However, DFT with exact exchange predicts dramatic improvement in performance for (Ni,Fe)OOH, leading to an overpotential of 0.42 V and a Tafel slope of 23 mV/decade (dec), in good agreement with experiments, 0.3–0.4 V and 30 mV/dec. We reveal that the high spin d 4 Fe(IV) leads to efficient formation of an active O radical intermediate, while the closed shell d 6 Ni(IV) catalyzes the subsequent O–O coupling, and thus it is the synergy between Fe and Ni that delivers the optimal performance for OER.

Authors:
ORCiD logo; ; ORCiD logo
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1438081
Alternate Identifier(s):
OSTI ID: 1540280
Grant/Contract Number:  
SC0004993
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 23; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology; Other Topics; density functional theory; B3PW91; PBE; electrocatalysis; reaction mechanism

Citation Formats

Xiao, Hai, Shin, Hyeyoung, and Goddard, III, William A. Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction. United States: N. p., 2018. Web. doi:10.1073/pnas.1722034115.
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Xiao, Hai, Shin, Hyeyoung, & Goddard, III, William A. Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction. United States. https://doi.org/10.1073/pnas.1722034115
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Xiao, Hai, Shin, Hyeyoung, and Goddard, III, William A. Mon . "Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction". United States. https://doi.org/10.1073/pnas.1722034115.
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@article{osti_1438081,
title = {Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction},
author = {Xiao, Hai and Shin, Hyeyoung and Goddard, III, William A.},
abstractNote = {The oxygen evolution reaction (OER) is critical to solar production of fuels, but the reaction mechanism underlying the performance for a best OER catalyst, Fe-doped NiOOH [(Ni,Fe)OOH], remains highly controversial. We used grand canonical quantum mechanics to predict the OER mechanisms including kinetics and thus overpotentials as a function of Fe content in (Ni,Fe)OOH catalysts. We find that density functional theory (DFT) without exact exchange predicts that addition of Fe does not reduce the overpotential much. However, DFT with exact exchange predicts dramatic improvement in performance for (Ni,Fe)OOH, leading to an overpotential of 0.42 V and a Tafel slope of 23 mV/decade (dec), in good agreement with experiments, 0.3–0.4 V and 30 mV/dec. We reveal that the high spin d 4 Fe(IV) leads to efficient formation of an active O radical intermediate, while the closed shell d 6 Ni(IV) catalyzes the subsequent O–O coupling, and thus it is the synergy between Fe and Ni that delivers the optimal performance for OER.},
doi = {10.1073/pnas.1722034115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 23,
volume = 115,
place = {United States},
year = {Mon May 21 00:00:00 EDT 2018},
month = {Mon May 21 00:00:00 EDT 2018}
}
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https://doi.org/10.1073/pnas.1722034115
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