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Research Article | Online first | Published: 11 April 2024

Unraveling the modulation essence of p bands in Co-based oxide stability on acidic oxygen evolution reaction

Show Author's Information Yafei Yang1,  Yihao Xu1,  Haiquan Liu1,  Qi Zhang1,  Boling Liu1,  Menghua Yang1,  Huan Dai1,  Zunjian Ke1,  Dong He1( ),  Xiaobo Feng2,3( ),  Xiangheng Xiao1( )
Department of Physics, Zhongnan Hospital of Wuhan University, Wuhan University, Wuhan 430072, China
School of Physics and Electronic Information, Yunnan Normal University, Kunming 650500, China
Yunnan Key Laboratory of Opto-electronic Information Technology, Kunming 650500, China
Keywords:
stability, oxygen evolution reaction, p-band modulation, acidic oxygen evolution reaction (OER)
Topics:
ElectrocatalystsOxygen evolution reaction
Cite this article:
Yang Y, Xu Y, Liu H, et al. Unraveling the modulation essence of p bands in Co-based oxide stability on acidic oxygen evolution reaction. Nano Research, 2024, https://doi.org/10.1007/s12274-024-6593-6
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Abstract Full text Electronic supplementary material About this article

The oxygen evolution reaction (OER) electrocatalysts, which can keep active for a long time in acidic media, are of great significance to proton exchange membrane water electrolyzers. Here, Ru-Co3O4 electrocatalysts with transition metal oxide Co3O4 as matrix and the noble metal Ru as doping element have been prepared through an ion exchange–pyrolysis process mediated by metal-organic framework, in which Ru atoms occupy the octahedral sites of Co3O4. Experimental and theoretical studies show that introduced Ru atoms have a passivation effect on lattice oxygen. The strong coupling between Ru and O causes a negative shift in the energy position of the O p-band centers. Therefore, the bonding activity of oxygen in the adsorbed state to the lattice oxygen is greatly passivated during the OER process, thus improving the stability of matrix material. In addition, benefiting from the modulating effect of the introduced Ru atoms on the metal active sites, the thermodynamic and kinetic barriers have been significantly reduced, which greatly enhances both the catalytic stability and reaction efficiency of Co3O4.


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Electronic supplementary material
About this article

Unraveling the modulation essence of p bands in Co-based oxide stability on acidic oxygen evolution reaction

Show Author's information Yafei Yang1, Yihao Xu1, Haiquan Liu1, Qi Zhang1, Boling Liu1, Menghua Yang1, Huan Dai1, Zunjian Ke1, Dong He1( ), Xiaobo Feng2,3( ), Xiangheng Xiao1( )
Department of Physics, Zhongnan Hospital of Wuhan University, Wuhan University, Wuhan 430072, China
School of Physics and Electronic Information, Yunnan Normal University, Kunming 650500, China
Yunnan Key Laboratory of Opto-electronic Information Technology, Kunming 650500, China

Abstract

The oxygen evolution reaction (OER) electrocatalysts, which can keep active for a long time in acidic media, are of great significance to proton exchange membrane water electrolyzers. Here, Ru-Co3O4 electrocatalysts with transition metal oxide Co3O4 as matrix and the noble metal Ru as doping element have been prepared through an ion exchange–pyrolysis process mediated by metal-organic framework, in which Ru atoms occupy the octahedral sites of Co3O4. Experimental and theoretical studies show that introduced Ru atoms have a passivation effect on lattice oxygen. The strong coupling between Ru and O causes a negative shift in the energy position of the O p-band centers. Therefore, the bonding activity of oxygen in the adsorbed state to the lattice oxygen is greatly passivated during the OER process, thus improving the stability of matrix material. In addition, benefiting from the modulating effect of the introduced Ru atoms on the metal active sites, the thermodynamic and kinetic barriers have been significantly reduced, which greatly enhances both the catalytic stability and reaction efficiency of Co3O4.

Keywords: stability, oxygen evolution reaction, p-band modulation, acidic oxygen evolution reaction (OER)

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Publication history
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Acknowledgements

Publication history

Received: 24 January 2024
Revised: 26 February 2024
Accepted: 26 February 2024
Published: 11 April 2024

Copyright

© Tsinghua University Press 2024

Acknowledgements

Acknowledgements

We acknowledge financial support from the National Natural Science Foundation of China (Nos. 12025503, U23B2072, and 12105208). The authors would like to acknowledge the beamlines BL20U in the Shanghai Synchrotron Radiation Facility (SSRF). The authors acknowledge the Super-computing Center of Wuhan University and University of Science and Technology of China for the numerical calculations support. We also acknowledge the Center for Electron Microscopy at Wuhan University for their substantial supports to JEM-F200.

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