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Core@shell bimetallic nanoparticle synthesis via anion coordination

Nature Chemistry volume 3, pages 478–483 (2011)Cite this article

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Abstract

Core@shell structured bimetallic nanoparticles are currently of immense interest due to their unique electronic, optical and catalytic properties. However, their synthesis is non-trivial. We report a new supramolecular route for the synthesis of core@shell nanoparticles, based on an anion coordination protocol—the first to function by binding the shell metal to the surface of the pre-formed primary metal core before reduction. The resultant gold/palladium and platinum/palladium core@shell nanoparticles have been characterized by aberration-corrected scanning transmission electron microscopy (as well as other techniques), giving striking atomic-resolution images of the core@shell architecture, and the unique catalytic properties of the structured nanoparticles have been demonstrated in a remarkable improvement of the selective production of industrially valuable chloroaniline from chloronitrobenzene.

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Figure 1: Diagrammatic representation of anion coordination synthetic strategy for core@shell bimetallic nanoparticles.
Figure 2: AC-HAADF-STEM images of bimetallic nanoparticles on carbon.
Figure 3: Reduction of 2-chloronitrobenzene (8) using Au/Pd bimetallic nanoparticles.

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Acknowledgements

C.J.S. thanks Johnson Matthey and the Engineering and Physical Sciences Research Council for a CASE Studentship. ICP-MS analysis was conducted by G. Nnorom-Junior and J. McNaught, XPS by R.A.P. Smith, and TEM by G. Goodlet, at Johnson Matthey Technology Centre. We would also like to thank R.E. Palmer for allowing the use of the aberration corrected STEM facilities at the University of Birmingham, UK.

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Authors and Affiliations

  1. Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK

    Christopher J. Serpell & Paul D. Beer

  2. Johnson Matthey Technology Centre, Blount's Court, Sonning Common, Reading, RG4 9NH, UK

    James Cookson & Dogan Ozkaya

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  1. Christopher J. Serpell
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Contributions

P.D.B. and J.C. conceived the project. P.D.B., J.C. and C.J.S. designed the experiments. C.J.S. conducted the experiments. D.O. performed aberration corrected-high-angle annular dark field-scanning tunnelling electron microscopy. All authors contributed to analysis of the data. C.J.S., J.C. and P.D.B. wrote the paper.

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Correspondence to Paul D. Beer.

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Crystallographic data for TBA-AuCl4 (CIF 21 kb)

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Crystallographic data for TBA2-Pd2Cl6 (CIF 30 kb)

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Serpell, C., Cookson, J., Ozkaya, D. et al. Core@shell bimetallic nanoparticle synthesis via anion coordination. Nature Chem 3, 478–483 (2011). https://doi.org/10.1038/nchem.1030

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