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Hybrid nanoscale inorganic cages

Nature Materials volume 9, pages 810–815 (2010)Cite this article

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Abstract

Cage structures exhibit inherent high symmetry and beauty, and both naturally occurring and synthetic molecular-scale cages have been discovered. Their characteristic high surface area and voids have led to their use as catalysts and catalyst supports, filtration media and gas storage materials1,2. Nanometre-scale cage structures have also been synthesized, notably noble-metal cube-shaped cages prepared by galvanic displacement with promising applications in drug delivery and catalysis3,4,5,6. Further functionality for nanostructures in general is provided by the concept of hybrid nanoparticles combining two disparate materials on the same system to achieve synergistic properties stemming from unusual material combinations7,8,9,10,11. We report the integration of the two powerful concepts of cages and hybrid nanoparticles. A previously unknown edge growth mechanism has led to a new type of cage-structured hybrid metal–semiconductor nanoparticle; a ruthenium cage was grown selectively on the edges of a faceted copper(I) sulphide nanocrystal, contrary to the more commonly observed facet and island growth modes of other hybrids7,12,13,14,15. The cage motif was extended by exploiting the open frame to achieve empty cages and cages containing other semiconductors. Such previously unknown nano-inorganic cage structures with variable cores and metal frames manifest new chemical, optical and electronic properties and demonstrate possibilities for uses in electrocatalysis.

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Figure 1: Preparation of Ru-NICed copper sulphide particles and empty Ru NICs.
Figure 2: Determination of the 3D shape of the cage structures.
Figure 3: XRD and absorbance spectra of Cu2S seeds and Ru-caged Cu1.96S particles.
Figure 4: H2O2 sensing with cages.
Figure 5: Cation exchange to give Ru-NICed CdS and PbS.

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Acknowledgements

Partial financial support by the Israel Science Foundation (grant 972/08), and the ERC grant DCENSY is acknowledged. U.B. thanks the Alfred and Erica Larisch Memorial Chair in Solar Energy. M.B.S. thanks the Minerva Fellowship program funded by the German Federal Ministry for Education and Research and the Sara Lee Schupf Postdoctoral Fellowship. The authors also thank D. Mandler for use of electrochemisty instrumentation.

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Authors and Affiliations

  1. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

    Janet E. Macdonald & Uri Banin

  2. The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

    Janet E. Macdonald, Inna Popov & Uri Banin

  3. Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Research Centre Juelich, 52425 Juelich, Germany

    Maya Bar Sadan & Lothar Houben

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  1. Janet E. Macdonald
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  2. Maya Bar Sadan
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Contributions

J.E.M. and U.B. designed the experiments and wrote the manuscript. J.E.M. carried out the experiments, materials characterization and analysis. I.P. assisted with HAADF-STEM and energy-dispersive X-ray spectroscopy measurements and provided commentary on the manuscript and materials analysis. M.B.S. carried out the tomography experiments and the analysis of its data and wrote parts of the manuscripts. L.H. wrote the tomographic processing software and assisted in the reconstruction, provided the aberration-corrected HAADF-STEM images and commented on the manuscript.

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Correspondence to Uri Banin.

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The authors declare no competing financial interests.

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Macdonald, J., Bar Sadan, M., Houben, L. et al. Hybrid nanoscale inorganic cages. Nature Mater 9, 810–815 (2010). https://doi.org/10.1038/nmat2848

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