Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires

Article metrics

Abstract

Crystal-phase engineering offers opportunities for the rational design and synthesis of noble metal nanomaterials with unusual crystal phases that normally do not exist in bulk materials. However, it remains a challenge to use these materials as seeds to construct heterometallic nanostructures with desired crystal phases and morphologies for promising applications such as catalysis. Here, we report a strategy for the synthesis of binary and ternary hybrid noble metal nanostructures. Our synthesized crystal-phase heterostructured 4H/fcc Au nanowires enable the epitaxial growth of Ru nanorods on the 4H phase and fcc-twin boundary in Au nanowires, resulting in hybrid Au–Ru nanowires. Moreover, the method can be extended to the epitaxial growth of Rh, Ru–Rh and Ru–Pt nanorods on the 4H/fcc Au nanowires to form unique hybrid nanowires. Importantly, the Au–Ru hybrid nanowires with tunable compositions exhibit excellent electrocatalytic performance towards the hydrogen evolution reaction in alkaline media.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Synthesis and characterization of Au–Ru NWs.
Fig. 2: Synthesis and characterization of Au–Rh NWs.
Fig. 3: Synthesis and characterization of Au–Ru–Rh NWs.
Fig. 4: Charactrization of HER activity and stability using Au–Ru NWs as electrocatalysts.

References

  1. 1.

    Gilroy, K. D., Ruditskiy, A., Peng, H.-C., Qin, D. & Xia, Y. Bimetallic nanocrystals: syntheses, properties, and applications. Chem. Rev. 116, 10414–10472 (2016).

  2. 2.

    Cortie, M. B. & McDonagh, A. M. Synthesis and optical properties of hybrid and alloy plasmonic nanoparticles. Chem. Rev. 111, 3713–3735 (2011).

  3. 3.

    Tedsree, K. et al. Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst. Nat. Nanotech. 6, 302–307 (2011).

  4. 4.

    Habas, S. E., Lee, H., Radmilovic, V., Somorjai, G. A. & Yang, P. Shaping binary metal nanocrystals through epitaxial seeded growth. Nat. Mater. 6, 692–697 (2007).

  5. 5.

    Fan, F.-R. et al. Epitaxial growth of heterogeneous metal nanocrystals: from gold nano-octahedra to palladium and silver nanocubes. J. Am. Chem. Soc. 130, 6949–6951 (2008).

  6. 6.

    Xia, Y., Xia, X. & Peng, H.-C. Shape-controlled synthesis of colloidal metal nanocrystals: thermodynamic versus kinetic products. J. Am. Chem. Soc. 137, 7947–7966 (2015).

  7. 7.

    Ringe, E., Van Duyne, R. P. & Marks, L. D. Kinetic and thermodynamic modified Wulff constructions for twinned nanoparticles. J. Phys. Chem. C. 117, 15859–15870 (2013).

  8. 8.

    Zhu, C. et al. Kinetically controlled overgrowth of Ag or Au on Pd nanocrystal seeds: from hybrid dimers to nonconcentric and concentric bimetallic nanocrystals. J. Am. Chem. Soc. 134, 15822–15831 (2012).

  9. 9.

    Xia, X., Wang, Y., Ruditskiy, A. & Xia, Y. Galvanic replacement: a simple and versatile route to hollow nanostructures with tunable and well-controlled properties. Adv. Mater. 25, 6313–6333 (2013).

  10. 10.

    Xia, Y., Xiong, Y., Lim, B. & Skrabalak, S. E. Shape-controlled synthesis of metal nanocrystals: simple chemistry meets complex physics? Angew. Chem. Int. Ed. 48, 60–103 (2009).

  11. 11.

    Jin, M., Zhang, H., Xie, Z. & Xia, Y. Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation. Energy Environ. Sci. 5, 6352–6357 (2012).

  12. 12.

    Gilroy, K. D., Hughes, R. A. & Neretina, S. Kinetically controlled nucleation of silver on surfactant-free gold seeds. J. Am. Chem. Soc. 136, 15337–15345 (2014).

  13. 13.

    Wang, Z. et al. Lattice-mismatch-induced twinning for seeded growth of anisotropic nanostructures. ACS Nano 9, 3307–3313 (2015).

  14. 14.

    Langille, M. R., Zhang, J., Personick, M. L., Li, S. & Mirkin, C. A. Stepwise evolution of spherical seeds into 20-fold twinned icosahedra. Science 337, 954 (2012).

  15. 15.

    Xia, Y., Gilroy, K. D., Peng, H.-C. & Xia, X. Seed-mediated growth of colloidal metal nanocrystals. Angew. Chem. Int. Ed. 56, 60–95 (2017).

  16. 16.

    Huang, X. et al. Synthesis of hexagonal close-packed gold nanostructures. Nat. Commun. 2, 292 (2011).

  17. 17.

    Fan, Z. et al. Stabilization of 4H hexagonal phase in gold nanoribbons. Nat. Commun. 6, 7684 (2015).

  18. 18.

    Fan, Z. et al. Synthesis of 4H/fcc noble multimetallic nanoribbons for electrocatalytic hydrogen evolution reaction. J. Am. Chem. Soc. 138, 1414–1419 (2016).

  19. 19.

    Fan, Z. et al. Epitaxial growth of unusual 4H hexagonal Ir, Rh, Os, Ru and Cu nanostructures on 4H Au nanoribbons. Chem. Sci. 8, 795–799 (2017).

  20. 20.

    An, H. et al. Unusual Rh nanocrystal morphology control by hetero-epitaxially growing Rh on Au@Pt nanowires with numerous vertical twinning boundaries. Nanoscale 7, 8309–8314 (2015).

  21. 21.

    Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410 (2016).

  22. 22.

    Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).

  23. 23.

    McKone, J. R., Sadtler, B. F., Werlang, C. A., Lewis, N. S. & Gray, H. B. Ni–Mo nanopowders for efficient electrochemical hydrogen evolution. ACS Catal. 3, 166–169 (2013).

  24. 24.

    Ma, L., Ting, L. R. L., Molinari, V., Giordano, C. & Yeo, B. S. Efficient hydrogen evolution reaction catalyzed by molybdenum carbide and molybdenum nitride nanocatalysts synthesized via the urea glass route. J. Mater. Chem. A 3, 8361–8368 (2015).

  25. 25.

    Laursen, A. B. et al. Nanocrystalline Ni5P4: a hydrogen evolution electrocatalyst of exceptional efficiency in both alkaline and acidic media. Energy Environ. Sci. 8, 1027–1034 (2015).

  26. 26.

    Wang, H. et al. Direct and continuous strain control of catalysts with tunable battery electrode materials. Science 354, 1031 (2016).

  27. 27.

    Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science 315, 493–497 (2007).

  28. 28.

    Wang, D. et al. Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 12, 81–87 (2013).

Download references

Acknowledgements

This work was supported by Ministry of Education (MOE) under AcRF Tier 2 (ARC 19/15, no. MOE2014-T2-2-093, MOE2015-T2-2-057, MOE2016-T2-2-103, MOE2017-T2-1-162) and AcRF Tier 1 (2016-T1-001-147, 2016-T1-002-051, 2017-T1-001-150) and Nanyang Technological University under a Start-Up Grant (M4081296.070.500000) in Singapore, the National Program on Key Basic Research Project (2014CB921002), the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB07030200), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (grant no. QYZDB-SSW-JSC035) and the National Natural Science Foundation of China (51522212, 51421002, 51672307). The authors acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore, for use of their electron microscopy facilities.

Author information

H.Z. proposed the research direction and guided the project. Q.L. and A.-L.W. conceived the idea and designed the experiments with H.Z., synthesized the materials, tested HER performance, analysed the data and drafted the manuscript. Y.G. and L.G. carried out STEM measurements. Ji.C. and J.L. carried out the EDS tomographic reconstructions. W.H., H.C., Ju.C., B.L., N.Y., W.N., J.W., Y.Y., X.Z., and Y.C. performed some supporting experiments. Z.F., X.-J.W. and S.L. helped to draft the manuscript. All authors have read the manuscript and agree with its content.

Correspondence to Lin Gu or Hua Zhang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary information

Supplementary synthesis and characterization details and analysis; Supplementary figures 1–19; Supplementary tables 1 & 2

Videos

Supplementary Video 1

Energy-dispersive X-ray spectroscopy tomographic reconstructions showing the architecture of the as-prepared Au–Ru nanowires

Supplementary Video 2

Energy-dispersive X-ray spectroscopy tomographic reconstructions showing the architecture of the as-prepared Au–Ru nanowires

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Further reading