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Intergrowth of Components and Ramps in Coffin-Shaped ZSM-5 Zeolite Crystals Unraveled by Focused Ion Beam-Assisted Transmission Electron Microscopy

  • Jiangbo Lu (a1), Maarten B.J. Roeffaers (a2), Evelyne Bartholomeeusen (a2), Bert F. Sels (a2) and Dominique Schryvers (a1)...


Scanning electron microscopy, focused ion beam (FIB), and transmission electron microscopy are combined to study the intergrowth of 90° rotational components and of ramps in coffin-shaped ZSM-5 crystals. The 90° rotational boundaries with local zig-zag features between different intergrowth components are observed in the main part of crystal. Also a new kind of displacement boundary is described. At the displacement boundary there is a shift of the unit cells along the boundary without a change in orientation. Based on lamellae prepared with FIB from different positions of the ramps and crystal, the orientation relationships between ramps and the main part of the crystal are studied and the three-dimensional morphology and growth mechanism of the ramp are illustrated.


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Agger, J.R., Hanif, N., Cundy, C.S., Wade, A.P., Dennison, S., Rawlinson, P.A. & Anderson, M.W. (2002). Silicalite crystal growth investigated by atomic force microscopy. J Am Chem Soc 125(3), 830839.
Aramburo, L.R., Karwacki, L., Cubillas, P., Asahina, S., de Winter, D.A.M., Drury, M.R., Buurmans, I.L.C., Stavitski, E., Mores, D., Daturi, M., Bazin, P., Dumas, P., Thibault-Starzyk, F., Post, J.A., Anderson, M.W., Terasaki, O. & Weckhuysen, B.M. (2011). The porosity, acidity, and reactivity of dealuminated zeolite ZSM-5 at the single particle level: The influence of the zeolite architecture. Chem Eur J 17(49), 1377313781.
De Cremer, G., Sels, B.F., De Vos, D.E., Hofkens, J. & Roeffaers, M.B.J. (2010). Fluorescence micro(spectro)scopy as a tool to study catalytic materials in action. Chem Soc Rev 39(12), 47034717.
Den Hollander, M.A., Wissink, M., Makkee, M. & Moulijn, J.A. (2002). Gasoline conversion: Reactivity towards cracking with equilibrated FCC and ZSM-5 catalysts. Appl Catal A 223(1-2), 85102.
Gonthier, S. & Thompson, R.W. (1994). Effects of seeding on zeolite crystallisation, and the growth behavior of seeds. In Studies in Surface Science and Catalysis, Jansen, J.C., Stöker, M., Karge, H.G. & Weitkamp, J. (Eds.), pp. 4373. Amsterdam: Elsevier.
Hay, D.G., Jaeger, H. & Wilshier, K.G. (1990). Systematic intergrowth in crystals of ZSM-5 zeolite. Zeolites 10(6), 571576.
Iwasaki, A., Hirata, M., Kudo, I. & Sano, T. (1996). Behavior of the (010) face of silicalite crystal. Zeolites 16(1), 3541.
Iwasaki, A., Hirata, M., Kudo, I., Sano, T., Sugawara, S., Ito, M. & Watanabe, M. (1995). In situ measurement of crystal growth rate of zeolite. Zeolites 15(4), 308314.
Iwasaki, A., Sano, T. & Kiyozumi, Y. (1998). Effect of additives on the growth behavior of silicalite crystal. Micropor Mesopor Mat 25(1-3), 119126.
Karwacki, L., de Winter, D.A.M., Aramburo, L.R., Lebbink, M.N., Post, J.A., Drury, M.R. & Weckhuysen, B.M. (2011). Architecture-dependent distribution of mesopores in steamed zeolite crystals as visualized by FIB-SEM tomography. Angew Chem Int Ed 50(6), 12941298.
Karwacki, L., Kox, M.H.F., Matthijs de Winter, D.A., Drury, M.R., Meeldijk, J.D., Stavitski, E., Schmidt, W., Mertens, M., Cubillas, P., John, N., Chan, A., Kahn, N., Bare, S.R., Anderson, M., Kornatowski, J. & Weckhuysen, B.M. (2009). Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers. Nat Mater 8(12), 959965.
Karwacki, L., Stavitski, E., Kox, M.H., Kornatowski, J. & Weckhuysen, B.M. (2007). Intergrowth structure of zeolite crystals as determined by optical and fluorescence microscopy of the template-removal process. Angew Chem Int Ed 46(38), 72287231.
Karwacki, L. & Weckhuysen, B.M. (2011). 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(9), 36813685.
Klapper, H. (2010). Generation and propagation of defects during crystal growth. In Springer Handbook of Crystal Growth, Dhanaraj, G., Byrappa, K., Prasad, V. & Dudley, M. (Eds.), pp. 93132. Heidelberg, Berlin: Springer.
Kox, M.H.F., Stavitski, E. & Weckhuysen, B.M. (2007). Nonuniform catalytic behavior of zeolite crystals as revealed by in situ optical microspectroscopy. Angew Chem Int Ed 46(20), 36523655.
Millward, G.R., Ramdas, S., Thomas, J.M. & Barlow, M.T. (1983). Evidence for semi-regularly ordered sequences of mirror and inversion symmetry planes in ZSM-5/ZSM-11 shape-selective zeolitic catalysts. J Chem Soc, Faraday Trans 2 79(7), 10751082.
Mueller, U. & Unger, K.K. (1988). Preliminary studies on the synthesis of alkaline-free large crystals of ZSM-5. Zeolites 8(2), 154156.
Price, G.D., Pluth, J.J., Smith, J.V., Bennett, J.M. & Patton, R.L. (1982). Crystal structure of tetrapropylammonium fluoride-containing precursor to fluoride silicalite. J Am Chem Soc 104(22), 59715977.
Roeffaers, M.B., Sels, B.F., Uji-I, H., Blanpain, B., L'Hoest, P., Jacobs, P.A., De Schryver, F.C., Hofkens, J. & De Vos, D.E. (2007). Space- and time-resolved visualization of acid catalysis in ZSM-5 crystals by fluorescence microscopy. Angew Chem Int Ed 46(10), 17061709.
Roeffaers, M.B.J., Ameloot, R., Baruah, M., Uji-I, H., Bulut, M., De Cremer, G., Müller, U., Jacobs, P.A., Hofkens, J., Sels, B.F. & De Vos, D.E. (2008a). Morphology of large ZSM-5 crystals unraveled by fluorescence microscopy. J Am Chem Soc 130(17), 57635772.
Roeffaers, M.B.J., Ameloot, R., Bons, A.-J., Mortier, W., De Cremer, G., de Kloe, R., Hofkens, J., De Vos, D.E. & Sels, B.F. (2008b). Relating pore structure to activity at the subcrystal level for ZSM-5: An electron backscattering diffraction and fluorescence microscopy study. J Am Chem Soc 130(41), 1351613517.
Roeffaers, M.B.J., de Cremer, G., Libeert, J., Ameloot, R., Dedecker, P., Bons, A.-J., Bückins, M., Martens, J.A., Sels, B.F., de Vos, D.E. & Hofkens, J. (2009). Super-resolution reactivity mapping of nanostructured catalyst particles. Angew Chem Int Ed 48(49), 92859289.
Stavitski, E., Drury, M.R., de Winter, D.A.M., Kox, M.H.F. & Weckhuysen, B.M. (2008). Intergrowth structure of zeolite crystals and pore orientation of individual subunits revealed by electron backscatter diffraction/focused ion beam experiments. Angew Chem Int Ed 47(30), 56375640.
Stavitski, E., Kox, M.H.F. & Weckhuysen, B.M. (2007). Revealing shape selectivity and catalytic activity trends within the pores of H-ZSM-5 crystals by time- and space-resolved optical and fluorescence microspectroscopy. Chem Eur J 13(25), 70577065.
Taylor, J.C., Miller, S.A. & Bibby, D.M. (1986). A study of decomposition methods for refinement of H+-ZSM5 zeolite with powder diffraction data. Z Kristallogr 176(3-4), 183192.
Tzoulaki, D., Heinke, L., Schmidt, W., Wilczok, U. & Karger, J. (2008). Exploring crystal morphology of nanoporous hosts from time-dependent guest profiles. Angew Chem Int Ed 47(21), 39543957.
Van der Veen, M.A., Sels, B.F., De Vos, D.E. & Verbiest, T. (2010). Localization of p-nitroaniline chains inside zeolite ZSM-5 with second-harmonic generation microscopy. J Am Chem Soc 132(19), 66306631.
Weckhuysen, B.M. (2009). Chemical imaging of spatial heterogeneities in catalytic solids at different length and time scales. Angew Chem Int Ed 48(27), 49104943.
Weidenthaler, C., Fischer, R.X., Shannon, R.D. & Medenbach, O. (1994). Optical investigations of intergrowth effects in the zeolite catalysts ZSM-5 and ZSM-8. J Phys Chem 98(48), 1268712694.
Wu, E.L., Lawton, S.L., Olson, D.H., Rohrman, A.C. & Kokotailo, G.T. (1979). ZSM-5-type materials. Factors affecting crystal symmetry. J Phys Chem 83(21), 27772781.
Wu, X. & Anthony, R.G. (1999). Alkylation of benzene with formaldehyde over ZSM-5. J Catal 184(1), 294297.


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Intergrowth of Components and Ramps in Coffin-Shaped ZSM-5 Zeolite Crystals Unraveled by Focused Ion Beam-Assisted Transmission Electron Microscopy

  • Jiangbo Lu (a1), Maarten B.J. Roeffaers (a2), Evelyne Bartholomeeusen (a2), Bert F. Sels (a2) and Dominique Schryvers (a1)...


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