Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction

Mengjie Liu; Hoje Chun; Tsung Cheng Yang; Sung Jun Hong; Chia Min Yang; Byungchan Han; Lawrence Yoon Suk Lee

doi:10.1021/acsnano.2c02324

Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction

Mengjie Liu, Hoje Chun, Tsung Cheng Yang, Sung Jun Hong, Chia Min Yang, Byungchan Han, Lawrence Yoon Suk Lee

Department of Chemical and Biomolecular Engineering

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

2 Citations (Scopus)

Abstract

The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate "encapsulation-substitution"strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.

Original language	English
Pages (from-to)	10657-10666
Number of pages	10
Journal	ACS Nano
Volume	16
Issue number	7
DOIs	https://doi.org/10.1021/acsnano.2c02324
Publication status	Published - 2022 Jul 26

Bibliographical note

Funding Information:
The authors gratefully acknowledge financial support from the Research Grants Council of the Hong Kong SAR, China (PolyU15217521), the Hong Kong Polytechnic University (Q-CDA3), the Ministry of Science and Technology, Taiwan (MOST 109-2113-M-007-018-MY3 and MOST 109-2634-F-007-023), and the Global Frontier Hybrid Interface Materials of National Research Foundation of Korea (2013M3A6B1078882). National Synchrotron Radiation Research Centre, Taiwan, is gratefully acknowledged for XAS characterizations.

Publisher Copyright:
© 2022 American Chemical Society.

All Science Journal Classification (ASJC) codes

Materials Science(all)
Engineering(all)
Physics and Astronomy(all)

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10.1021/acsnano.2c02324

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title = "Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction",

abstract = "The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate {"}encapsulation-substitution{"}strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.",

author = "Mengjie Liu and Hoje Chun and Yang, {Tsung Cheng} and Hong, {Sung Jun} and Yang, {Chia Min} and Byungchan Han and Lee, {Lawrence Yoon Suk}",

note = "Funding Information: The authors gratefully acknowledge financial support from the Research Grants Council of the Hong Kong SAR, China (PolyU15217521), the Hong Kong Polytechnic University (Q-CDA3), the Ministry of Science and Technology, Taiwan (MOST 109-2113-M-007-018-MY3 and MOST 109-2634-F-007-023), and the Global Frontier Hybrid Interface Materials of National Research Foundation of Korea (2013M3A6B1078882). National Synchrotron Radiation Research Centre, Taiwan, is gratefully acknowledged for XAS characterizations. Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

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doi = "10.1021/acsnano.2c02324",

language = "English",

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AU - Liu, Mengjie

AU - Chun, Hoje

AU - Yang, Tsung Cheng

AU - Hong, Sung Jun

AU - Yang, Chia Min

AU - Han, Byungchan

AU - Lee, Lawrence Yoon Suk

N1 - Funding Information: The authors gratefully acknowledge financial support from the Research Grants Council of the Hong Kong SAR, China (PolyU15217521), the Hong Kong Polytechnic University (Q-CDA3), the Ministry of Science and Technology, Taiwan (MOST 109-2113-M-007-018-MY3 and MOST 109-2634-F-007-023), and the Global Frontier Hybrid Interface Materials of National Research Foundation of Korea (2013M3A6B1078882). National Synchrotron Radiation Research Centre, Taiwan, is gratefully acknowledged for XAS characterizations. Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/7/26

Y1 - 2022/7/26

N2 - The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate "encapsulation-substitution"strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.

AB - The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate "encapsulation-substitution"strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.

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Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction

Abstract

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