Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Incorporation of clusters within inorganic materials through their addition during nucleation steps

Abstract

Nanomaterials are known to display chemical and physical behaviours that are different from those of their bulk counterparts, but assembly processes in the sub-nanometre region are difficult to control. The early growth of nanomaterials is typically thought to involve two separate steps: nucleation and the growth stage, as described by the LaMer model. Control of the shape and size of the final structure is typically determined during the growth stage by interactions between the nuclei and surrounding monomers. Here, we show that clusters with well-defined structures, such as polyoxometalates, can intervene at the nucleation stage of nickel oxysulfide and nickel–cobalt hydroxide by co-assembling with nuclei to produce uniform binary assemblies. Those can, in turn, incorporate a third, or also a fourth, type of nanocluster to form ternary or quaternary assemblies, respectively. Both binary and ternary assemblies are shown to serve as efficient atomic-site catalysts for room-temperature gasoline desulfurization and stereoselective catalytic reactions.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic illustrations of two different growth pathways.
Fig. 2: Morphological images of CAMs.
Fig. 3: Growth pathways in the presence and absence of additional clusters.
Fig. 4: Images of various kinds of ternary NiSx-NiOx CAMs.
Fig. 5: Stability studies.

Similar content being viewed by others

Data availability

The authors declare that all the data supporting the findings of this study are available within the paper and the Supplementary Information and/or from the authors upon reasonable request.

References

  1. LaMer, V. K. & Dinegar, R. H. Theory, production and mechanism of formation of monodispersed hydrosols. J. Am. Chem. Soc. 72, 4847–4854 (1950).

    Article  CAS  Google Scholar 

  2. 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).

    Article  CAS  Google Scholar 

  3. Tsung, C. K. et al. Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation. J. Am. Chem. Soc. 131, 5816–5822 (2009).

    Article  CAS  Google Scholar 

  4. Talapin, D. V., Lee, J. S., Kovalenko, M. V. & Shevchenko, E. V. Prospects of colloidal nanocrystals for electronic and optoelectronic applications. Chem. Rev. 110, 389–458 (2010).

    Article  CAS  Google Scholar 

  5. Shevchenko, E. V., Talapin, D. V., Kotov, N. A., O’Brien, S. & Murray, C. B. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006).

    Article  CAS  Google Scholar 

  6. Kalsin, A. M. et al. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 312, 420–424 (2006).

    Article  CAS  Google Scholar 

  7. Wang, X., Zhuang, J., Peng, Q. & Li, Y. A general strategy for nanocrystal synthesis. Nature 437, 121–124 (2005).

    Article  CAS  Google Scholar 

  8. Srivastava, S. et al. Light-controlled self-assembly of semiconductor nanoparticles into twisted ribbons. Science 327, 1355–1359 (2010).

    Article  CAS  Google Scholar 

  9. Ye, X. et al. Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals. Nat. Commun. 6, 10052 (2015).

    Article  Google Scholar 

  10. Kim, S. & Bawendi, M. G. Oligomeric ligands for luminescent and stable nanocrystal quantum dots. J. Am. Chem. Soc. 125, 14652–14653 (2003).

    Article  CAS  Google Scholar 

  11. Zhang, J., Liu, J., Huang, J. L., Kim, P. & Lieber, C. M. Creation of nanocrystals through a solid–solid phase transition induced by an STM tip. Science 274, 757–760 (1996).

    Article  CAS  Google Scholar 

  12. Udayabhaskararao, T. et al. Tunable porous nanoallotropes prepared by post-assembly etching of binary nanoparticle superlattices. Science 358, 514–518 (2017).

    Article  CAS  Google Scholar 

  13. Siegel, R. W. Cluster-assembled nanophase materials. Annu. Rev. Mater. Sci. 21, 559–578 (1991).

    Article  CAS  Google Scholar 

  14. Claridge, S. A. et al. Cluster-assembled materials. ACS Nano 3, 244–25 (2009).

    Article  CAS  Google Scholar 

  15. Morphew, D., Shaw, J., Avins, C. & Chakrabarti, D. Programming hierarchical self-assembly of patchy particles into colloidal crystals via colloidal molecules. ACS Nano 12, 2355–2364 (2018).

    Article  CAS  Google Scholar 

  16. Ni, B. & Wang, X. Chemistry and properties at a sub-nanometer scale. Chem. Sci. 7, 3978–3991 (2016).

    Article  CAS  Google Scholar 

  17. Yang, Y. et al. Atomic-level molybdenum oxide nanorings with full-spectrum absorption and photoresponsive properties. Nat. Commun. 8, 1559 (2017).

    Article  Google Scholar 

  18. Hu, S., Liu, H., Wang, P. & Wang, X. Inorganic nanostructures with sizes down to 1 nm: a macromolecule analogue. J. Am. Chem. Soc. 135, 11115–11124 (2013).

    Article  CAS  Google Scholar 

  19. He, J., Liu, H., Xu, B. & Wang, X. Highly flexible sub-1 nm tungsten oxide nanobelts as efficient desulfurization catalysts. Small 11, 1144–1149 (2015).

    Article  CAS  Google Scholar 

  20. Liu, H., Gong, Q., Yue, Y., Guo, L. & Wang, X. Sub-1 nm nanowire based superlattice showing high strength and low modulus. J. Am. Chem. Soc. 139, 8579–8585 (2017).

    Article  CAS  Google Scholar 

  21. Ni, B., Liu, H., Wang, P. P., He, J. & Wang, X. General synthesis of inorganic single-walled nanotubes. Nat. Commun. 6, 8756 (2015).

    Article  CAS  Google Scholar 

  22. Liu, J., Yang, Y., Ni, B., Li, H. & Wang, X. Fullerene-Like nickel oxysulfide hollow nanospheres as bifunctional electrocatalysts for water splitting. Small 13, 1602637 (2017).

    Article  Google Scholar 

  23. Ni, B. & Wang, X. Edge overgrowth of spiral bimetallic hydroxides ultrathin-nanosheets for water oxidation. Chem. Sci. 6, 3572–3576 (2015).

    Article  CAS  Google Scholar 

  24. Heinz, H., Vaia, R. A., Farmer, B. L. & Naik, R. R. Accurate simulation of surfaces and interfaces of face-centered cubic metals using 12−6 and 9−6 Lennard–Jones potentials. J. Phys. Chem. C 112, 17281–17290 (2008).

    Article  CAS  Google Scholar 

  25. Nisar, A., Zhuang, J. & Wang, X. Construction of amphiphilic polyoxometalate mesostructures as a highly efficient desulfurization catalyst. Adv. Mater. 23, 1130–1135 (2011).

    Article  CAS  Google Scholar 

  26. Nisar, A., Lu, Y., Zhuang, J. & Wang, X. Polyoxometalate nanocone nanoreactors: magnetic manipulation and enhanced catalytic performance. Angew. Chem. Int. Ed. 50, 3187–3192 (2011).

    Article  CAS  Google Scholar 

  27. Teschner, D. et al. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science 320, 86–89 (2008).

    Article  CAS  Google Scholar 

  28. Venkatesan, R. et al. Palladium nanoparticle catalysts in ionic liquids: synthesis, characterisation and selective partial hydrogenation of alkynes to Z-alkenes. J. Mater. Chem. 21, 3030 (2011).

    Article  CAS  Google Scholar 

  29. Shen, R. et al. Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid. J. Am. Chem. Soc. 133, 17037–17044 (2011).

    Article  CAS  Google Scholar 

  30. Chan, C. W. A. et al. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation. Nat. Commun. 5, 5787 (2014).

    Article  CAS  Google Scholar 

  31. Brunet, J. J. & Caubere, P. Activation of reducing agents. Sodium hydride containing complex reducing agents. 20. Pdc, a new, very selective heterogeneous hydrogenation catalyst. J. Org. Chem. 49, 4058–4060 (1984).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank L. Gu and Y. Han for their help with HRTEM characterization, Y. Huang and J. Zhang for help with providing POM samples and H. Li for help with MALDI-TOF MS. X.W. is thankful for support from the National Key R&D Program of China (2017YFA0700101, 2016YFA0202801) and the NSFC (21431003).

Author information

Authors and Affiliations

Authors

Contributions

X.W. proposed and guided the project. J.L. designed, planned and carried out the experiments and analysed data. W.S. and S.L. performed the MD simulations. B.N. performed HRTEM tests of samples. Y.Y. and J.Z. provided the synthesis method for PtP nanoclusters.

Corresponding authors

Correspondence to Shuzhou Li or Xun Wang.

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.

Supporting information

Supporting Information

Materials and methods; Supplementary Figs. 1–49; Supplementary Tables 1–17; Molecular dynamics (MD) simulations; Supplementary references

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Shi, W., Ni, B. et al. Incorporation of clusters within inorganic materials through their addition during nucleation steps. Nat. Chem. 11, 839–845 (2019). https://doi.org/10.1038/s41557-019-0303-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-019-0303-0

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing