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Nano Research 2023, 16(5): 6622-6631 https://doi.org/10.1007/s12274-023-5399-2
Research Article | Issue | Published: 12 January 2023

Size and near-surface engineering in weak-oxidative confined space to fabricate 4 nm L10-PtCo@Pt nanoparticles for oxygen reduction reaction

Show Author's Information Yifei Liao1,2,3,  Lishan Peng4,5,  Chaoling Wu2,3,  Yigang Yan1,3,  Haijiao Xie6,  Yungui Chen1,3( ),  Yao Wang1,3( )
Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610065, China
Department of Advanced Energy Materials, College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China
Engineering Research Center of Alternative Energy Materials & Devices, Ministry of Education, Chengdu 610065, China
School of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand
Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China
Hangzhou Yanqu Information Technology Co., Ltd., Hangzhou 310003, China
Keywords:
oxygen reduction reaction, core–shell structure, intermetallics, near-surface engineering
Topics:
Electrocatalysts
An erratum to this article is available online at https://doi.org/10.1007/s12274-023-5599-9
Cite this article:
Liao Y, Peng L, Wu C, et al. Size and near-surface engineering in weak-oxidative confined space to fabricate 4 nm L10-PtCo@Pt nanoparticles for oxygen reduction reaction. Nano Research, 2023, 16(5): 6622-6631. https://doi.org/10.1007/s12274-023-5399-2
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Abstract Full text Electronic supplementary material About this article

The near-surface structure of the Pt-based alloy including the surface and subsurface structures is prominent to their electrocatalytic performance. Modulating the near-surface structure of PtCo intermetallics with small particle size could efficiently optimize the binding force between Pt and oxygen and finally enhance its oxygen reduction reaction (ORR) performance. Here we simultaneously achieve the size controlling and surface modulation of intermetallic nanoparticles (NPs) in a weak-oxidative confined space with abundant uncoordinated oxygen atoms. 1–2 atomic layers of concave Pt-rich surface were successfully constructed on 4 nm L10-PtCo core after removing Co–O species which is derived from the segregation of the subsurface Co to the surface induced by the uncoordinated oxygen atoms. Owing to the elaborate structure, PtCo-1000/C catalyst shows significant improvement in both activity (1.290 A∙mgPt−1 and 1.529 mA∙cmPt−2 at 0.9 V vs. reversible hydrogen electrode (RHE)) and stability (85.2% of initial mass activity after accelerated degression tests (ADTs)) even the production is scaled up to gram level. Density functional theory calculations suggest that the cave Pt site optimizes the protonation of *O, which finally boosts the ORR performance.


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Electronic supplementary material
About this article

Size and near-surface engineering in weak-oxidative confined space to fabricate 4 nm L10-PtCo@Pt nanoparticles for oxygen reduction reaction

Show Author's information Yifei Liao1,2,3, Lishan Peng4,5, Chaoling Wu2,3, Yigang Yan1,3, Haijiao Xie6, Yungui Chen1,3( ), Yao Wang1,3( )
Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610065, China
Department of Advanced Energy Materials, College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China
Engineering Research Center of Alternative Energy Materials & Devices, Ministry of Education, Chengdu 610065, China
School of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand
Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China
Hangzhou Yanqu Information Technology Co., Ltd., Hangzhou 310003, China

Abstract

The near-surface structure of the Pt-based alloy including the surface and subsurface structures is prominent to their electrocatalytic performance. Modulating the near-surface structure of PtCo intermetallics with small particle size could efficiently optimize the binding force between Pt and oxygen and finally enhance its oxygen reduction reaction (ORR) performance. Here we simultaneously achieve the size controlling and surface modulation of intermetallic nanoparticles (NPs) in a weak-oxidative confined space with abundant uncoordinated oxygen atoms. 1–2 atomic layers of concave Pt-rich surface were successfully constructed on 4 nm L10-PtCo core after removing Co–O species which is derived from the segregation of the subsurface Co to the surface induced by the uncoordinated oxygen atoms. Owing to the elaborate structure, PtCo-1000/C catalyst shows significant improvement in both activity (1.290 A∙mgPt−1 and 1.529 mA∙cmPt−2 at 0.9 V vs. reversible hydrogen electrode (RHE)) and stability (85.2% of initial mass activity after accelerated degression tests (ADTs)) even the production is scaled up to gram level. Density functional theory calculations suggest that the cave Pt site optimizes the protonation of *O, which finally boosts the ORR performance.

Keywords: oxygen reduction reaction, core–shell structure, intermetallics, near-surface engineering

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Publication history
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Acknowledgements

Publication history

Received: 16 August 2022
Revised: 24 November 2022
Accepted: 10 December 2022
Published: 12 January 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgment

This work was financially supported by the National Natural Science Foundation of China (Nos. 22279082 and 21908148), the Natural Science Foundation of Sichuan (No. 2022NSFSC1247), and the Fundamental Research Funds for the Central Universities. The authors thank the Institute of New Energy and Low-Carbon Technology, Sichuan University, for SEM image capturing and they are grateful to Dr. Yingming Zhu for his help.

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