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Title: Reaction mechanism for oxygen evolution on RuO 2, IrO 2, and RuO 2@IrO 2 core-shell nanocatalysts

Iridium dioxide, IrO 2, is second to the most active RuO 2 catalyst for the oxygen evolution reaction (OER) in acid, and is used in proton exchange membrane water electrolyzers due to its high durability. In order to improve the activity of IrO 2-based catalysts, we prepared RuO 2@IrO 2 core-shell nanocatalysts using carbon-supported Ru as the template. At 1.48 V, the OER specific activity of RuO 2@IrO 2 is threefold that of IrO 2. While the activity volcano plots over wide range of materials have been reported, zooming into the top region to clarify the rate limiting steps of most active catalysts is important for further activity enhancement. Here, we verified theory-proposed sequential water dissociation pathway in which the O—O bond forms on a single metal site, not via coupling of two adsorbed intermediates, by fitting measured polarization curves using a kinetic equation with the free energies of adsorption and activation as the parameters. Consistent with theoretical calculations, we show that the OER activities of IrO 2 and RuO 2@IrO 2 are limited by the formation of O adsorbed phase, while the OOH formation on the adsorbed O limits the reaction rate on RuO 2.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [3] ;  [3] ;  [1] ; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  3. Proton OnSite, Wallingford, CT (United States)
Publication Date:
Report Number(s):
BNL-114508-2017-JAAM
Journal ID: ISSN 1572-6657
Grant/Contract Number:
SC0012704; FG02-12ER86531; AC02-06CH11357; 21336003; 2014CB239703
Type:
Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 819; Journal Issue: C; Journal ID: ISSN 1572-6657
Publisher:
Elsevier
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); National Natural Science Foundation of China (NNSF); National Basic Research Program of China; National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Electrolysis; RuO2; IrO2; Core-shell; Oxygen evolution reaction mechanism
OSTI Identifier:
1425009
Alternate Identifier(s):
OSTI ID: 1460967

Ma, Zhong, Zhang, Yu, Liu, Shizhong, Xu, Wenqian, Wu, Lijun, Hsieh, Yu-Chi, Liu, Ping, Zhu, Yimei, Sasaki, Kotaro, Renner, Julie N., Ayers, Katherine E., Adzic, Radoslav R., and Wang, Jia X.. Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts. United States: N. p., Web. doi:10.1016/j.jelechem.2017.10.062.
Ma, Zhong, Zhang, Yu, Liu, Shizhong, Xu, Wenqian, Wu, Lijun, Hsieh, Yu-Chi, Liu, Ping, Zhu, Yimei, Sasaki, Kotaro, Renner, Julie N., Ayers, Katherine E., Adzic, Radoslav R., & Wang, Jia X.. Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts. United States. doi:10.1016/j.jelechem.2017.10.062.
Ma, Zhong, Zhang, Yu, Liu, Shizhong, Xu, Wenqian, Wu, Lijun, Hsieh, Yu-Chi, Liu, Ping, Zhu, Yimei, Sasaki, Kotaro, Renner, Julie N., Ayers, Katherine E., Adzic, Radoslav R., and Wang, Jia X.. 2017. "Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts". United States. doi:10.1016/j.jelechem.2017.10.062.
@article{osti_1425009,
title = {Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts},
author = {Ma, Zhong and Zhang, Yu and Liu, Shizhong and Xu, Wenqian and Wu, Lijun and Hsieh, Yu-Chi and Liu, Ping and Zhu, Yimei and Sasaki, Kotaro and Renner, Julie N. and Ayers, Katherine E. and Adzic, Radoslav R. and Wang, Jia X.},
abstractNote = {Iridium dioxide, IrO2, is second to the most active RuO2 catalyst for the oxygen evolution reaction (OER) in acid, and is used in proton exchange membrane water electrolyzers due to its high durability. In order to improve the activity of IrO2-based catalysts, we prepared RuO2@IrO2 core-shell nanocatalysts using carbon-supported Ru as the template. At 1.48 V, the OER specific activity of RuO2@IrO2 is threefold that of IrO2. While the activity volcano plots over wide range of materials have been reported, zooming into the top region to clarify the rate limiting steps of most active catalysts is important for further activity enhancement. Here, we verified theory-proposed sequential water dissociation pathway in which the O—O bond forms on a single metal site, not via coupling of two adsorbed intermediates, by fitting measured polarization curves using a kinetic equation with the free energies of adsorption and activation as the parameters. Consistent with theoretical calculations, we show that the OER activities of IrO2 and RuO2@IrO2 are limited by the formation of O adsorbed phase, while the OOH formation on the adsorbed O limits the reaction rate on RuO2.},
doi = {10.1016/j.jelechem.2017.10.062},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 819,
place = {United States},
year = {2017},
month = {10}
}