Safeguarding the RuO2 phase against lattice oxygen oxidation during acidic water electrooxidation

Haneul Jin; Songa Choi; Gi Joo Bang; Taehyun Kwon; Hee Soo Kim; Su Ji Lee; Yongju Hong; Dong Wook Lee; Hyun S. Park; Hionsuck Baik; Yousung Jung; Sung Jong Yoo; Kwangyeol Lee

doi:10.1039/d1ee02636d

Safeguarding the RuO₂ phase against lattice oxygen oxidation during acidic water electrooxidation

Haneul Jin, Songa Choi, Gi Joo Bang, Taehyun Kwon, Hee Soo Kim, Su Ji Lee, Yongju Hong, Dong Wook Lee, Hyun S. Park, Hionsuck Baik, Yousung Jung, Sung Jong Yoo, Kwangyeol Lee

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

28 Citations (Scopus)

Abstract

Defective RuO₂ possesses excellent initial activity toward the oxygen evolution reaction in acidic water electrooxidation due to the involvement of lattice oxygens, which, however, is the very reason for the accelerated dissolution of Ru species. Therefore, it is crucial to steer the electrochemical oxygen evolution towards the adsorbate evolution mechanism (AEM) for improved durability of the RuO₂ phase in acidic electrolytes. Herein, we developed a method to mix Pt atoms with the RuO₂ matrix in a controlled manner by exploiting the oxophilicity of certain first-row transition metals in pulling out the Pt atoms in Pt-based nanorod@Ru under oxidative conditions. The resulting nanorod-shaped PtCo-RuO₂/C showed 212.6 ± 5.3 mV overpotential at 10 mA cm⁻² in a half-cell test and exhibited mass activity and long-term stability that greatly surpass those of Pt-RuO₂/C and commercial Ir/C. Microscopic and spectroscopic analyses and density functional theory calculation of the nanocatalysts before and after OER cycles were conducted to scrutinize the role of Pt dopants for the observed durability and activity, revealing that Pt dopants promote *OOH adsorption and deprotonation, thereby limiting Ru overoxidation during OER cycles. When PtCo-RuO₂/C was applied to a proton-exchange membrane water electrolyzer, it showed a single-cell performance of 3.7 A mg_Ru+Pt⁻¹ at 2.0

Original language	English
Pages (from-to)	1119-1130
Number of pages	12
Journal	Energy and Environmental Science
Volume	15
Issue number	3
DOIs	https://doi.org/10.1039/d1ee02636d
Publication status	Published - 2021 Nov 12

ASJC Scopus subject areas

Environmental Chemistry
Renewable Energy, Sustainability and the Environment
Nuclear Energy and Engineering
Pollution

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1039/d1ee02636d

Cite this

@article{aabab07bfadd479897b707fb612e1a68,

title = "Safeguarding the RuO2 phase against lattice oxygen oxidation during acidic water electrooxidation",

abstract = "Defective RuO2 possesses excellent initial activity toward the oxygen evolution reaction in acidic water electrooxidation due to the involvement of lattice oxygens, which, however, is the very reason for the accelerated dissolution of Ru species. Therefore, it is crucial to steer the electrochemical oxygen evolution towards the adsorbate evolution mechanism (AEM) for improved durability of the RuO2 phase in acidic electrolytes. Herein, we developed a method to mix Pt atoms with the RuO2 matrix in a controlled manner by exploiting the oxophilicity of certain first-row transition metals in pulling out the Pt atoms in Pt-based nanorod@Ru under oxidative conditions. The resulting nanorod-shaped PtCo-RuO2/C showed 212.6 ± 5.3 mV overpotential at 10 mA cm−2 in a half-cell test and exhibited mass activity and long-term stability that greatly surpass those of Pt-RuO2/C and commercial Ir/C. Microscopic and spectroscopic analyses and density functional theory calculation of the nanocatalysts before and after OER cycles were conducted to scrutinize the role of Pt dopants for the observed durability and activity, revealing that Pt dopants promote *OOH adsorption and deprotonation, thereby limiting Ru overoxidation during OER cycles. When PtCo-RuO2/C was applied to a proton-exchange membrane water electrolyzer, it showed a single-cell performance of 3.7 A mgRu+Pt−1 at 2.0",

author = "Haneul Jin and Songa Choi and Bang, {Gi Joo} and Taehyun Kwon and Kim, {Hee Soo} and Lee, {Su Ji} and Yongju Hong and Lee, {Dong Wook} and Park, {Hyun S.} and Hionsuck Baik and Yousung Jung and Yoo, {Sung Jong} and Kwangyeol Lee",

note = "Funding Information: This work was supported by the National Research Foundation (NRF) of Korea (Grant No. NRF-2020R1A2B5B03002475, NRF-2019R1A6A1A11044070, NRF-2019M3E6A1064709, NRF-2021M3H4A1A02049916, NRF-2018M1A2A2061975, NRF-2021M3H4A1A02042948, and NRF-2020M3E6A1044370), the New & Renewable Energy Core Technology Program of KETEP (20203020030010), and the Korea Basic Science Institute (KBSI) (Project No. C123000). The authors thank KBSI for the usage of their HRTEM. Experiments at PLS-II were supported in part by MSICT and POSTECH. Publisher Copyright: {\textcopyright} 2021 The Royal Society of Chemistry.",

year = "2021",

month = nov,

day = "12",

doi = "10.1039/d1ee02636d",

language = "English",

volume = "15",

pages = "1119--1130",

journal = "Energy and Environmental Science",

issn = "1754-5692",

publisher = "Royal Society of Chemistry",

number = "3",

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TY - JOUR

T1 - Safeguarding the RuO2 phase against lattice oxygen oxidation during acidic water electrooxidation

AU - Jin, Haneul

AU - Choi, Songa

AU - Bang, Gi Joo

AU - Kwon, Taehyun

AU - Kim, Hee Soo

AU - Lee, Su Ji

AU - Hong, Yongju

AU - Lee, Dong Wook

AU - Park, Hyun S.

AU - Baik, Hionsuck

AU - Jung, Yousung

AU - Yoo, Sung Jong

AU - Lee, Kwangyeol

N1 - Funding Information: This work was supported by the National Research Foundation (NRF) of Korea (Grant No. NRF-2020R1A2B5B03002475, NRF-2019R1A6A1A11044070, NRF-2019M3E6A1064709, NRF-2021M3H4A1A02049916, NRF-2018M1A2A2061975, NRF-2021M3H4A1A02042948, and NRF-2020M3E6A1044370), the New & Renewable Energy Core Technology Program of KETEP (20203020030010), and the Korea Basic Science Institute (KBSI) (Project No. C123000). The authors thank KBSI for the usage of their HRTEM. Experiments at PLS-II were supported in part by MSICT and POSTECH. Publisher Copyright: © 2021 The Royal Society of Chemistry.

PY - 2021/11/12

Y1 - 2021/11/12

N2 - Defective RuO2 possesses excellent initial activity toward the oxygen evolution reaction in acidic water electrooxidation due to the involvement of lattice oxygens, which, however, is the very reason for the accelerated dissolution of Ru species. Therefore, it is crucial to steer the electrochemical oxygen evolution towards the adsorbate evolution mechanism (AEM) for improved durability of the RuO2 phase in acidic electrolytes. Herein, we developed a method to mix Pt atoms with the RuO2 matrix in a controlled manner by exploiting the oxophilicity of certain first-row transition metals in pulling out the Pt atoms in Pt-based nanorod@Ru under oxidative conditions. The resulting nanorod-shaped PtCo-RuO2/C showed 212.6 ± 5.3 mV overpotential at 10 mA cm−2 in a half-cell test and exhibited mass activity and long-term stability that greatly surpass those of Pt-RuO2/C and commercial Ir/C. Microscopic and spectroscopic analyses and density functional theory calculation of the nanocatalysts before and after OER cycles were conducted to scrutinize the role of Pt dopants for the observed durability and activity, revealing that Pt dopants promote *OOH adsorption and deprotonation, thereby limiting Ru overoxidation during OER cycles. When PtCo-RuO2/C was applied to a proton-exchange membrane water electrolyzer, it showed a single-cell performance of 3.7 A mgRu+Pt−1 at 2.0

AB - Defective RuO2 possesses excellent initial activity toward the oxygen evolution reaction in acidic water electrooxidation due to the involvement of lattice oxygens, which, however, is the very reason for the accelerated dissolution of Ru species. Therefore, it is crucial to steer the electrochemical oxygen evolution towards the adsorbate evolution mechanism (AEM) for improved durability of the RuO2 phase in acidic electrolytes. Herein, we developed a method to mix Pt atoms with the RuO2 matrix in a controlled manner by exploiting the oxophilicity of certain first-row transition metals in pulling out the Pt atoms in Pt-based nanorod@Ru under oxidative conditions. The resulting nanorod-shaped PtCo-RuO2/C showed 212.6 ± 5.3 mV overpotential at 10 mA cm−2 in a half-cell test and exhibited mass activity and long-term stability that greatly surpass those of Pt-RuO2/C and commercial Ir/C. Microscopic and spectroscopic analyses and density functional theory calculation of the nanocatalysts before and after OER cycles were conducted to scrutinize the role of Pt dopants for the observed durability and activity, revealing that Pt dopants promote *OOH adsorption and deprotonation, thereby limiting Ru overoxidation during OER cycles. When PtCo-RuO2/C was applied to a proton-exchange membrane water electrolyzer, it showed a single-cell performance of 3.7 A mgRu+Pt−1 at 2.0

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DO - 10.1039/d1ee02636d

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