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Core–shell strain structure of zeolite microcrystals

Nature Materials volume 12, pages 729–734 (2013)Cite this article

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Abstract

Zeolites are crystalline aluminosilicate minerals featuring a network of 0.3–1.5-nm-wide pores, used in industry as catalysts for hydrocarbon interconversion, ion exchangers, molecular sieves and adsorbents1. For improved applications, it is highly useful to study the distribution of internal local strains because they sensitively affect the rates of adsorption and diffusion of guest molecules within zeolites2,3. Here, we report the observation of an unusual triangular deformation field distribution in ZSM-5 zeolites by coherent X-ray diffraction imaging4, showing the presence of a strain within the crystal arising from the heterogeneous core–shell structure, which is supported by finite element model calculation and confirmed by fluorescence measurement. The shell is composed of H-ZSM-5 with intrinsic negative thermal expansion5 whereas the core exhibits a different thermal expansion behaviour due to the presence of organic template residues, which usually remain when the starting materials are insufficiently calcined. Engineering such strain effects could have a major impact on the design of future catalysts.

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Figure 1: CXD patterns and three-dimensional image of a ZSM-5 zeolite crystal.
Figure 2: Internal phase images depending on calcination condition as a function of temperature.
Figure 3: Measured thermal expansion behaviour of ZSM-5 calcined at 550 °C (A), 450 °C (B), and as-synthesized before calcination (C).
Figure 4: FEA simulation of displacement distribution at 200 °C with core–shell structure and confocal fluorescence microscope image.

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References

  1. Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002).

    Article  CAS  Google Scholar 

  2. Smit, B. & Maesen, T. L. M. Towards a molecular understanding of shape selectivity. Nature 451, 671–678 (2008).

    Article  CAS  Google Scholar 

  3. Kärger, J. Single-file diffusion in zeolites. Mol. Sieves Sci. Technol. 7, 329–366 (2008).

    Article  Google Scholar 

  4. Robinson, I. & Harder, R. Coherent X-ray diffraction imaging of strain at the nanoscale. Nature Mater. 8, 291–298 (2009).

    Article  CAS  Google Scholar 

  5. Park, S. H., Kunstleve, R-W. G., Graetsch, H. & Gies, H. The thermal expansion of the zeolites MFI, AFI, DOH, DDR, and MTN in their calcined and as synthesized forms. Stud. Surf. Sci. Catal. 105, 1989–1994 (1997).

    Article  Google Scholar 

  6. Lai, Z. et al. Microstructural optimization of a zeolite membrane for organic vapor separation. Science 300, 456–460 (2003).

    CAS  Google Scholar 

  7. Choi, J. et al. Grain boundary defect elimination in a zeolite membrane by rapid thermal processing. Science 325, 590–593 (2009).

    Article  CAS  Google Scholar 

  8. Pham, T. C. T., Kim, H. S. & Yoon, K. B. Growth of uniformly oriented silica MFI and BEA zeolite films on substrates. Science 334, 1533–1538 (2011).

    Article  CAS  Google Scholar 

  9. Lee, J. S., Lee, Y.-J., Tae, E. L., Park, Y. S. & Yoon, K. B. Synthesis of zeolite as ordered multicrystal arrays. Science 301, 818–821 (2003).

    Article  CAS  Google Scholar 

  10. Caro, J. & Noack, M. in Advances in Nanoporous Materials, Vol. 1 (ed. Ernst, S.) Ch. 1, 1–96 (Elsevier, 2009).

    Google Scholar 

  11. Caro, J. & Noack, M. Zeolite membranes—Recent developments and progress. Micropor. Mesopor. Mater. 115, 215–233 (2008).

    Article  CAS  Google Scholar 

  12. O’Brien-Abraham, J. & Lin, J. Y. S. in Zeolites in Industrial Separation and Catalysis (ed. Kulprathipanja, S.) Ch. 10, 307–329 (Wiley, 2010).

    Book  Google Scholar 

  13. O’Brien-Abraham, J., Kanezashi, M. & Lin, Y. S. Effects of adsorption-induced microstructural changes on separation on xylene isomers through MFI-type zeolite membranes. J. Membr. Sci. 320, 505–513 (2008).

    Article  Google Scholar 

  14. Hedlund, J., Jareman, F., Bons, A-J. & Anthonis, M. A masking technique for high quality MFI membranes. J. Membr. Sci. 222, 163–179 (2003).

    Article  CAS  Google Scholar 

  15. Bein, T. Synthesis and applications of molecular sieve layers and membranes. Chem. Mater. 8, 1636–1653 (1996).

    Article  CAS  Google Scholar 

  16. Jeong, H. -K., Lai, Z., Tsapatsis, M. & Hanson, J. C. Strain of MFI crystals in membranes: An in situ synchrotron X-ray study. Micropor. Mesopor. Mater. 84, 332–337 (2005).

    Article  CAS  Google Scholar 

  17. Marinkovic, B. A. et al. Complex thermal expansion properties of Al-containing HZSM-5 zeolite: A X-ray diffraction, neutron diffraction and thermogravimetry study. Micropor. Mesopor. Mater. 111, 110–116 (2008).

    Article  CAS  Google Scholar 

  18. Chao, K-J., Lin, J-C., Wang, Y. & Lee, G. H. Single crystal structure refinement of TPA ZSM-5 zeolite. Zeolites 6, 35–38 (1986).

    Article  CAS  Google Scholar 

  19. Gao, X., Yeh, C. Y. & Angevine, P. Mechanistic study of organic template removal from ZSM-5 precursors. Micropor. Mesopor. Mater. 70, 27–35 (2004).

    Article  CAS  Google Scholar 

  20. Gualtieri, M. L., Gualtieri, A. F. & Hedlund, J. The influence of heating rate on template removal in silicalite-1: An in situ HT-XRPD study. Micropor. Mesopor. Mater. 89, 1–8 (2006).

    Article  Google Scholar 

  21. Sen, S., Wusirika, R. R. & Youngman, R. E. High temperature thermal expansion behavior of H[Al]ZSM-5 zeolites: The role of Brønsted sites. Micropor. Mesopor. Mater. 87, 217–223 (2006).

    Article  CAS  Google Scholar 

  22. Pfeifer, M. A., Williams, G. J., Vartanyants, I. A., Harder, R. & Robinson, I. K. Three-dimensional mapping of a deformation field inside a nanocrystal. Nature 442, 63–66 (2006).

    Article  CAS  Google Scholar 

  23. Newton, M. C., Leake, S. J., Harder, R. & Robinson, I. K. Three-dimensional imaging of strain in a single ZnO nanorod. Nature Mater. 9, 120–124 (2010).

    Article  CAS  Google Scholar 

  24. Fienup, J. R. Phase retrieval algorithms: a comparison. Appl. Opt. 21, 2758–2769 (1982).

    Article  CAS  Google Scholar 

  25. Karwacki, L. & Weckhuysen, B. M. New insight in the template decomposition process of large zeolite ZSM-5 crystals: An in situ UV-Vis/fluorescence micro-spectroscopy study. Phys. Chem. Chem. Phys. 13, 3681–3685 (2011).

    Article  CAS  Google Scholar 

  26. Ballmoos, R. & Meier, W. M. Zoned aluminium distribution in synthetic zeolite ZSM-5. Nature 289, 782–783 (1981).

    Article  Google Scholar 

Download references

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education and the Ministry of Science, ICT & Future Planning of Korea (Nos. 2007-0053982, 2011-0012251 and 2008-0062606, CELA-NCRC), Sogang University Research Grant of 2012 and an ERC FP7 Advanced Grant 227711. W.C. was also supported by a Hi Seoul Science/Humanities Fellowship from the Seoul Scholarship Foundation. K.B.Y. thanks the NRF project No. 2012M1A2A2671784. G.X. and I.K.R. were supported by the ‘Nanoscupture’ advanced grant from the European Research Council. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Science, under Contract No. DE-AC02-06CH11357.

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Author notes

  1. Nak Cheon Jeong

    Present address: Present address: Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science & Technology (DGIST), Daegu 711–873, Korea,

Authors and Affiliations

  1. Department of Physics, Sogang University, Seoul 121-742, Korea

    Wonsuk Cha, Hyun-jun Park & Hyunjung Kim

  2. Department of Chemistry, Sogang University, Seoul 121-742, Korea

    Nak Cheon Jeong, Tung Cao Thanh Pham & Kyung Byung Yoon

  3. Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-742, Korea

    Sanghoon Song, Kyung Byung Yoon & Hyunjung Kim

  4. Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Ross Harder

  5. Department of Life Sciences, Sogang University, Seoul 121-742, Korea

    Bobae Lim & Jungho Kim

  6. London Centre for Nanotechnology, University College, London WC1H 0AH, UK

    Gang Xiong & Ian K. Robinson

  7. Pohang Accelerator Laboratory, Pohang 790-784, Korea

    Docheon Ahn

  8. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Ian McNulty

  9. Research Complex at Harwell, Didcot, Oxford OX11 0DE, UK

    Ian K. Robinson

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Contributions

H.K. supervised and coordinated all aspects of the project. ZSM-5 growth was carried out by N.C.J. and T.C.T.P. under the supervision of K.B.Y. Coherent X-ray diffraction measurements were carried out by W.C., S.S., H-j.P., R.H., I.K.R. and H. K. CDI data analysis was carried out by W.C. and R.H. Energy-dispersive X-ray spectra measurements were performed by T.C.T.P. and W.C. Confocal fluorescence microscopy measurements were carried out by B.L. and W.C. under the supervision of J.K. and H.K. Powder diffraction measurements were carried out by W.C., S.S., H-j.P. and D.A. and data analysis done by W.C. H-j.P. and D.A. Finite element analysis calculation was carried out by G.X., R.H. and W.C. under the supervision of I.K.R and H.K. W.C., R.H. and I.M. carried out X-ray microfluorescence measurements. W.C., K.B.Y., I.K.R. and H.K. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Hyunjung Kim.

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Cha, W., Jeong, N., Song, S. et al. Core–shell strain structure of zeolite microcrystals. Nature Mater 12, 729–734 (2013). https://doi.org/10.1038/nmat3698

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