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Mechanistic principles of nanoparticle evolution to zeolite crystals

Nature Materials volume 5, pages 400–408 (2006)Cite this article

Abstract

Precursor nanoparticles that form spontaneously on hydrolysis of tetraethylorthosilicate in aqueous solutions of tetrapropylammonium (TPA) hydroxide evolve to TPA-silicalite-1, a molecular-sieve crystal that serves as a model for the self-assembly of porous inorganic materials in the presence of organic structure-directing agents. The structure and role of these nanoparticles are of practical significance for the fabrication of hierarchically ordered porous materials and molecular-sieve films, but still remain elusive. Here we show experimental findings of nanoparticle and crystal evolution during room-temperature ageing of the aqueous suspensions that suggest growth by aggregation of nanoparticles. A kinetic mechanism suggests that the precursor nanoparticle population is distributed, and that the 5-nm building units contributing most to aggregation only exist as an intermediate small fraction. The proposed oriented-aggregation mechanism should lead to strategies for isolating or enhancing the concentration of crystal-like nanoparticles.

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Figure 1: Composition space.
Figure 2: Characterization of precursor nanoparticles from C3.
Figure 3: Emergence and evolution of silicalite-1 crystals in C3.
Figure 4: TEM characterization of TPA-silicalite-1 crystals present in C3 after 305 days of ageing (crystal yield less than 5%).
Figure 5: Attachment of precursor nanoparticles on mica surfaces by liquid phase in situ AFM imaging.
Figure 6: Simulation data from mathematical model of nanoparticle ageing and growth mechanism.

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Acknowledgements

Financial support for this work was provided by NSF (NIRT CTS-0103010 and CTS-05 22518). The HRTEM work was supported in part by NSF-MRI EAR-0320641 and the MRSEC Program of NSF under Award Number DMR-0212302. M.K. acknowledges support from NSF (DMS-041386). Characterization was carried out at the Minnesota Characterization Facility, which receives support from NSF through the National Nanotechnology Infrastructure Network. Numerical simulations were carried out using the facilities of the Supercomputing Institute for Digital Simulation and Advanced Computation at the University of Minnesota. We thank A. Parr for lending us the SAXSess instrument; F. S. Bates for providing access to SANS analysis at NIST and for helpful discussions; and R. Bedard, D. G. Vlachos, V. Nikolakis, R. F. Lobo and V. Hatzimanikatis for input at various stages of this work.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, University of Minnesota, 151 Amundson Hall, 421 Washington Avenue SE, Minneapolis, Minnesota, 55455, USA

    Tracy M. Davis, Timothy O. Drews, Harikrishnan Ramanan, Chuan He, Jingshan Dong, Efrosini Kokkoli, Alon V. McCormick & Michael Tsapatsis

  2. Department of Chemistry, University of Minnesota, B-4, 139 Smith Hall, 207 Pleasant Street SE, Minneapolis, Minnesota, 55455, USA

    Harikrishnan Ramanan & R. Lee Penn

  3. Anton Paar GmbH, Anton-Paar-Str. 20, A-8054, Graz, Austria

    Heimo Schnablegger

  4. Department of Mathematics and Statistics, University of Massachusetts, 710 North Pleasant Street, Amherst, Massachusetts, 01003, USA

    Markos A. Katsoulakis

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  1. Tracy M. Davis
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Correspondence to Michael Tsapatsis.

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Davis, T., Drews, T., Ramanan, H. et al. Mechanistic principles of nanoparticle evolution to zeolite crystals. Nature Mater 5, 400–408 (2006). https://doi.org/10.1038/nmat1636

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