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Achieving stable surface structures of metal catalysts is an extreme challenge for obtaining long-term durability and meeting industrial application requirements. We report a new class of metal catalyst, Pt-rich PtCu heteroatom subnanoclusters epitaxially grown on an octahedral PtCu alloy/Pt skin matrix (PtCu1.60), for the oxygen reduction reaction (ORR) in an acid electrolyte. The PtCu1.60/C exhibits an 8.9-fold enhanced mass activity (1.42 A·mgPt−1) over that of commercial Pt/C (0.16 A·mgPt−1). The PtCu1.60/C exhibits 140,000 cycles durability without activity decline and surface PtCu cluster stability owing to unique structure derived from the matrix and epitaxial growth pattern, which effectively prevents the agglomeration of clusters and loss of near-surface active sites. Structure characterization and theoretical calculations confirm that Pt-rich PtCu clusters favor ORR activity and thermodynamic stability. In room-temperature polymer electrolyte membrane fuel cells, the PtCu1.60/C shows enhanced performance and delivers a power density of 154.1/318.8 mW·cm2 and 100 h/50 h durability without current density decay in an air/O2 feedstock.


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PtCu subnanoclusters epitaxial on octahedral PtCu/Pt skin matrix as ultrahigh stable cathode electrocatalysts for room-temperature hydrogen fuel cells

Show Author's information Fengling Zhao1Lirong Zheng2Qiang Yuan1( )Qinghua Zhang5Tian Sheng4( )Xiaotong Yang1Lin Gu5Xun Wang3( )
State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, College of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China
Beijing Synchrotron Radiation Facility Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Key Lab of Organic Optoelectronics & Molecular Engineering, Tsinghua University, Beijing 100084, China
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, China
Chinese Academy of Sciences and Beijing National Laboratory for Condensed Matter Physics, Beijing 100190, China

Abstract

Achieving stable surface structures of metal catalysts is an extreme challenge for obtaining long-term durability and meeting industrial application requirements. We report a new class of metal catalyst, Pt-rich PtCu heteroatom subnanoclusters epitaxially grown on an octahedral PtCu alloy/Pt skin matrix (PtCu1.60), for the oxygen reduction reaction (ORR) in an acid electrolyte. The PtCu1.60/C exhibits an 8.9-fold enhanced mass activity (1.42 A·mgPt−1) over that of commercial Pt/C (0.16 A·mgPt−1). The PtCu1.60/C exhibits 140,000 cycles durability without activity decline and surface PtCu cluster stability owing to unique structure derived from the matrix and epitaxial growth pattern, which effectively prevents the agglomeration of clusters and loss of near-surface active sites. Structure characterization and theoretical calculations confirm that Pt-rich PtCu clusters favor ORR activity and thermodynamic stability. In room-temperature polymer electrolyte membrane fuel cells, the PtCu1.60/C shows enhanced performance and delivers a power density of 154.1/318.8 mW·cm2 and 100 h/50 h durability without current density decay in an air/O2 feedstock.

Keywords: oxygen reduction reaction, epitaxial growth, core–shell nanostructure, PtCu alloy, hydrogen fuel cells

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Publication history
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Acknowledgements

Publication history

Received: 13 July 2022
Revised: 16 August 2022
Accepted: 08 September 2022
Published: 03 November 2022
Issue date: February 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21571038, 21903001, and 22035004), the National Key R&D Program of China (No. 2017YFA0700101), Education Department of Guizhou Province (No. 2021312), Foundation of Guizhou Province (No. 2019-5666), Science Foundation for Aftergraduated Students of Guizhou Province (No. YJSKYJJ2021020), National Science Foundation of Anhui Province (No. 1908085QB58), State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University, No. 202009), and the Open Fund of the Key Lab of Organic Optoelectronics & Molecular Engineering (Tsinghua University).

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