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Hierarchical nanofabrication of microporous crystals with ordered mesoporosity

Nature Materials volume 7, pages 984–991 (2008)Cite this article

Abstract

Shaped zeolite nanocrystals and larger zeolite particles with three-dimensionally ordered mesoporous (3DOm) features hold exciting technological implications for manufacturing thin, oriented molecular sieve films and realizing new selective, molecularly accessible and robust catalysts. A recognized means for controlled synthesis of such nanoparticulate and imprinted materials revolves around templating approaches, yet identification of an appropriately versatile template has remained elusive. Because of their highly interconnected pore space, ordered mesoporous carbon replicas serve as conceptually attractive materials for carrying out confined synthesis of zeolite crystals. Here, we demonstrate how a wide range of crystal morphologies can be realized through such confined growth within 3DOm carbon, synthesized by replication of colloidal crystals composed of size-tunable (about 10–40 nm) silica nanoparticles. Confined crystal growth within these templates leads to size-tunable, uniformly shaped silicalite-1 nanocrystals as well as 3DOm-imprinted single-crystal zeolite particles. In addition, novel crystal morphologies, consisting of faceted crystal outgrowths from primary crystalline particles have been discovered, providing new insight into constricted crystal growth mechanisms underlying confined synthesis.

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Figure 1: Elucidating handles for controlling silica nanoparticle size.
Figure 2: Formation of tunable colloidal crystal templates.
Figure 3: Synthesis of 3DOm carbon templates for confining crystal growth.
Figure 4: Isolatable and faceted silicalite-1 nanocrystals.
Figure 5: 3DOm-imprinted silicalite-1 single crystals.

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Acknowledgements

The authors gratefully acknowledge support for this work from the National Science Foundation (CMMI-0707610). The authors also acknowledge T. M. Davis for cryo-TEM images taken of the nanoparticle sols. Characterization was carried out at the Minnesota Characterization Facility, which receives support from the NSF through the National Nanotechnology Infrastructure Network.

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Authors and Affiliations

  1. Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, USA

    Wei Fan, Mark A. Snyder, Sandeep Kumar, Pyung-Soo Lee, Alon V. McCormick & Michael Tsapatsis

  2. Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA

    Won Cheol Yoo, R. Lee Penn & Andreas Stein

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  1. Wei Fan
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Correspondence to Michael Tsapatsis.

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Fan, W., Snyder, M., Kumar, S. et al. Hierarchical nanofabrication of microporous crystals with ordered mesoporosity. Nature Mater 7, 984–991 (2008). https://doi.org/10.1038/nmat2302

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