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Synthesis and Characterization of Pd@MxCu1−x (M=Au, Pd, and Pt) Nanocages with Porous Walls and a Yolk–Shell Structure through Galvanic Replacement Reactions

Authors

  • Shuifen Xie,

    1. The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, School of Chemistry & Biochemistry and School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (USA)
    2. State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P.R. China)
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  • Prof. Mingshang Jin,

    1. Center for Materials Chemistry, Frontier Institute of Science and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049 (P.R. China)
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  • Dr. Jing Tao,

    1. Condensed Matter Physics & Materials Science Department, Brookhaven National Laboratory, Upton, New York 11973 (USA)
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  • Dr. Yucai Wang,

    1. The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, School of Chemistry & Biochemistry and School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (USA)
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  • Prof. Zhaoxiong Xie,

    1. State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 (P.R. China)
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  • Dr. Yimei Zhu,

    1. Condensed Matter Physics & Materials Science Department, Brookhaven National Laboratory, Upton, New York 11973 (USA)
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  • Prof. Younan Xia

    Corresponding author
    1. The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, School of Chemistry & Biochemistry and School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (USA)
    • The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, School of Chemistry & Biochemistry and School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (USA)
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Abstract

This paper describes the synthesis of Pd@MxCu1−x (M=Au, Pd, and Pt) nanocages with a yolk–shell structure through galvanic replacement reactions that involve Pd@Cu core–shell nanocubes as sacrificial templates and ethylene glycol as the solvent. Compared with the most commonly used templates based on Ag, Cu offers a much lower reduction potential (0.34 versus 0.80 V), making the galvanic reaction more easily to conduct, even at room temperature. Our structural and compositional characterizations indicated that the products were hollow inside, and each one of them contained porous M–Cu alloy walls and a Pd cube in the interior. For the Pd@AuxCu1−x yolk–shell nanocages, they displayed broad extinction peaks extending from the visible to the near-IR region. Our mechanistic study revealed that the dissolution of the Cu shell preferred to start from the slightly truncated corners and then progressed toward the interior, because the Cu {100} side faces were protected by a surface capping layer of hexadecylamine. This galvanic approach can also be extended to generating other hollow metal nanostructures by using different combinations of Cu nanostructures and salt precursors.

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