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Cu–Ni core–shell nanoparticles: structure, stability, electronic, and magnetic properties: a spin-polarized density functional study

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Abstract

Bimetallic core–shell nanoparticles (CSNPs) have attracted great interest not only because of their superior stability, selectivity, and catalytic activity but also due to their tunable properties achieved by changing the morphology, sequence, and sizes of both core and shell. In this study, the structure, stability, charge transfer, electronic, and magnetic properties of 13-atom and 55-atom Cu and Cu–Ni CSNPs were investigated using the density functional theory (DFT) calculations. The results show that Ni@Cu CSNPs with a Cu surface shell are more energetically favorable than Cu@Ni CSNPs with a Ni surface shell. Interestingly, three-shell Ni@Cu12@Ni42 is more stable than two-shell Cu13@Ni42, while two-shell Ni13@Cu42 is more stable than three-shell Cu@Ni12@Cu42. Analysis of Bader charge illustrates that the charge transfer increases from Cu core to Ni shell in Cu@Ni NPs, while it decreases from Ni core to Cu shell in Ni@Cu NPs. Furthermore, the charge transfer results that d-band states have larger shift toward the Fermi level for the Ni@Cu CSNPs with Cu surface shell, while the Cu@Ni CSNPs with Ni surface shell have similar d-band state curves and d-band centers with the monometallic Ni NPs. In addition, the Cu–Ni CSNPs possess higher magnetic moment when the Ni atoms aggregated at core region of CSNPs, while having lower magnetic moment when the Ni atoms segregate on surface region. The change of the Cu atom location in CSNPs has a weak effect on the total magnetic moment. Our findings provide useful insights for the design of bimetallic core–shell catalysts.

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Acknowledgments

This work was supported by the National Natural Science Foundations of China (21203094, 21373112) and China Postdoctoral Science Foundation (2016M591834).

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Authors and Affiliations

  1. School of Chemistry and Molecular Engineering, Institute of Advanced Synthesis (IAS), Nanjing Tech University, Nanjing, 211816, People’s Republic of China

    Qiang Wang, Xinyan Wang, Jianlan Liu & Yanhui Yang

  2. Technology Center, Shanghai Meishan Iron & Steel Co. Ltd., Nanjing, Jiangsu, 210039, People’s Republic of China

    Xinyan Wang

  3. School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, 637459, Singapore

    Yanhui Yang

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  1. Qiang Wang
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Correspondence to Qiang Wang.

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Funding

This study was funded by the National Natural Science Foundations of China (21203094, 21373112) and China Postdoctoral Science Foundation (2016M591834).

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The authors declare that they have no conflict of interest.

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Wang, Q., Wang, X., Liu, J. et al. Cu–Ni core–shell nanoparticles: structure, stability, electronic, and magnetic properties: a spin-polarized density functional study. J Nanopart Res 19, 25 (2017). https://doi.org/10.1007/s11051-016-3731-4

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