Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts
Abstract
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. 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 materials have been reported, zooming into the top region to clarify the rate limiting steps of currently most active catalysts is important for further developing advanced OER catalysts. 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.
- Authors:
-
[1];
[1];
[1]
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
- Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
- Proton OnSite, Wallingford, CT (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Natural Science Foundation of China (NNSF); Major Basic Research Program of China; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1425009
- Alternate Identifier(s):
- OSTI ID: 1460967; OSTI ID: 1549442
- Report Number(s):
- BNL-114508-2017-JAAM
Journal ID: ISSN 1572-6657
- Grant/Contract Number:
- SC0012704; FG02-12ER86531; AC02-06CH11357; 21336003; 2014CB239703
- Resource 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Electrolysis; RuO2; IrO2; Core-shell; Oxygen evolution reaction mechanism
Citation Formats
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., 2017.
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. https://doi.org/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. Sat .
"Reaction mechanism for oxygen evolution on RuO2, IrO2, and RuO2@IrO2 core-shell nanocatalysts". United States. https://doi.org/10.1016/j.jelechem.2017.10.062. https://www.osti.gov/servlets/purl/1425009.
@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. 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 materials have been reported, zooming into the top region to clarify the rate limiting steps of currently most active catalysts is important for further developing advanced OER catalysts. 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 = {Sat Oct 28 00:00:00 EDT 2017},
month = {Sat Oct 28 00:00:00 EDT 2017}
}
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