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Core–shell strain structure of zeolite microcrystals



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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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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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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The authors declare no competing financial interests.

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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).

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