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
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
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
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
LaMer, V. K. & Dinegar, R. H. Theory, production and mechanism of formation of monodispersed hydrosols. J. Am. Chem. Soc. 72, 4847–4854 (1950).
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).
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).
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).
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).
Kalsin, A. M. et al. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 312, 420–424 (2006).
Wang, X., Zhuang, J., Peng, Q. & Li, Y. A general strategy for nanocrystal synthesis. Nature 437, 121–124 (2005).
Srivastava, S. et al. Light-controlled self-assembly of semiconductor nanoparticles into twisted ribbons. Science 327, 1355–1359 (2010).
Ye, X. et al. Structural diversity in binary superlattices self-assembled from polymer-grafted nanocrystals. Nat. Commun. 6, 10052 (2015).
Kim, S. & Bawendi, M. G. Oligomeric ligands for luminescent and stable nanocrystal quantum dots. J. Am. Chem. Soc. 125, 14652–14653 (2003).
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).
Udayabhaskararao, T. et al. Tunable porous nanoallotropes prepared by post-assembly etching of binary nanoparticle superlattices. Science 358, 514–518 (2017).
Siegel, R. W. Cluster-assembled nanophase materials. Annu. Rev. Mater. Sci. 21, 559–578 (1991).
Claridge, S. A. et al. Cluster-assembled materials. ACS Nano 3, 244–25 (2009).
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).
Ni, B. & Wang, X. Chemistry and properties at a sub-nanometer scale. Chem. Sci. 7, 3978–3991 (2016).
Yang, Y. et al. Atomic-level molybdenum oxide nanorings with full-spectrum absorption and photoresponsive properties. Nat. Commun. 8, 1559 (2017).
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).
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).
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).
Ni, B., Liu, H., Wang, P. P., He, J. & Wang, X. General synthesis of inorganic single-walled nanotubes. Nat. Commun. 6, 8756 (2015).
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).
Ni, B. & Wang, X. Edge overgrowth of spiral bimetallic hydroxides ultrathin-nanosheets for water oxidation. Chem. Sci. 6, 3572–3576 (2015).
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).
Nisar, A., Zhuang, J. & Wang, X. Construction of amphiphilic polyoxometalate mesostructures as a highly efficient desulfurization catalyst. Adv. Mater. 23, 1130–1135 (2011).
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).
Teschner, D. et al. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science 320, 86–89 (2008).
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).
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).
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).
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).
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
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
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
About this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41557-019-0303-0
This article is cited by
-
Inorganic ionic polymerization: From biomineralization to materials manufacturing
Nano Research (2024)
-
Current Understanding on the Unique Relaxation Dynamics of Sub-nanometer Materials and Their Structure-Property Relationships
Chemical Research in Chinese Universities (2023)
-
High-entropy Metal Oxide-polyoxometalate-palladium Sub-1 nm Nanowires for Semi-hydrogenation Reaction of Alkynes
Chemical Research in Chinese Universities (2023)
-
Nanoclusters as Synthons for Unit-Cell-Size Comparable One-Dimensional Nanostructures
Chemical Research in Chinese Universities (2023)
-
Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores
Nature Chemistry (2022)