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Zeolite coatings and composites

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Structured zeolite containing composite materials – preparation

and properties



Prof. W. SCHWIEGER

Chemical Reaction Engineering

Friedrich-Alexander-University Erlangen-Nuremberg





Since the late eighties, there has been a rising interest in the development of zeolite

coatings. Zeolite coatings are defined as composite materials, comprising a carrier on which

zeolite crystals are physically or chemically bonded. Supporting zeolite onto carriers or

substrates of different nature, composition and structure/architecture represents a great

improvement concerning the technical applicability of zeolitic materials in traditional and

emerging fields like catalysis, adsorption, separation and sensors. The zeolite-supported

composite leads to performances that are beyond the limitations of unsupported zeolites, by

adding mechanical strength, a structuring function and novel functionalities. Indeed, the

combination of different materials (zeolite and carrier) with different properties can lead to

important synergies, allowing for the manufacturing of multifunctional composites, and

broadening the range of applications of zeolitic materials.

The aim of the contribution is to offer an overview on special coating techniques,

highlighting their synthesis, properties, and potential applications.

Hierarchical porous structures1,2, combining the benefits of different pore-size

regimes. Materials with combinations of micro-/mesopores4, micro-/macropores5, meso-

/macropores6 or porosity spreading up to the three orders7 have been synthesized, generally

employing two different approaches. Template-directed synthesis utilizes the inherent

porosity of temporary/sacrificial templates (artificial or biological) to structure hierarchical

porous inorganic frameworks by an imprinting process8. Differently, the coating approach

yields hierarchical porous composites by deposition or in-situ synthesis of micro- or meso-

porous frameworks onto porous carriers9,10.

In the development of hierarchical porous structure, zeolites1 are playing a major role.

Many efforts have been concentrated in realizing supported zeolite films for membrane

technology11 and zeolite composites or coatings for catalytic and adsorption application12. The

great number of different porous carriers which can be used and the huge number of zeolite

types make it possible to finely tailor materials for specific technical applications10,13. More

recently interests have been also given to self-supporting porous zeolitic frameworks14,

leading also to the development of hierarchical bioinspired architectures, utilizing zeolites as

building blocks to mimic natural or biological architectures3,15.

References



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

2. Shin, Y., Liu, J., Wang, L.-Q., Nie, Z., Samuels, W. D., Fryxell, G. E. & Exarhos, G. J., Ordered

Hierarchical Porous Materials: Towards Tunable Size- and Shape-Selective Microcavities in

Nanoporous Channels, Angewandte Chemie International Edition 39, 2702-2707 (2000).

3. Valtchev, V., Smaihi, M., Faust, A. C. & Vidal, L. Biomineral-silica-induced zeolitization of

Equisetum Arverse, Angew. Chem. Int. Ed. 42, 2782-2785 (2003).

4. Tao, Y., Kanoh, H. & Kaneko, K. ZSM-5 monolith of uniform mesoporous channels, J. Am. Chem.

Soc. 125 6044-6045 (2003).

5. Scheffler, F., Schwieger, W., Freude, D., Liu, H., Heyer, W. & Janowski, F. Transformation of

porous glass beads into MFI-type containing beads, Microporous Mesoporous Mater. 55, 181-191

(2002); Meyer, U., Larsson, A., Hentze, H.-P. & Caruso, R. A., Templating of porous polymeric

beads to form porous silica and titania spheres, Adv. Mater. 13, 1259-1263 (2002); Holland, B. T.,

Abrams, L. & Stein, A. Dual templating of macroporous silicates with zeolitic microporous

frameworks, J. Am. Chem. Soc. 121, 4308-4309 (1999).

6. Dong, A., Wang, Y., Tang, Y., Zhang, Y., Ren, N. & Gao Z. Mechanically stable zeolite monoliths

with three-dimensional ordered macropores by the transformation of mesoporous silica spheres,

Adv. Mater. 14, 1506-1510 (2002); Davis, S. A., Burkett, S. L., Mendelson, N. H. & Mann, S.

Bacterial templating of ordered macrostructures in silica and silica-surfactant mesophases, Nature

385, 420-423 (1997).

7. Rhodes, K. H., Davis, S. A., Caruso, F., Zhang, B. and Mann, S. Hierarchical assembly of zeolite

nanoparticles into ordered macroporous monoliths using core-shell building blocks, Chem. Mater.

12, 2832-2834 (2000).

8. Lee, Y.-J., Lee, J. S., Park, Y. S. & Yoon , K. B. Synthesis of large monolithic zeolite foams with

variable macropore architectures, Adv. Mater. 13, 1259-1263 (2001).

9. Scheffler, M., Gambaryan-Roisman, T., Zeschky, J., Scheffler, F. & Greil, P. Self-foamed cellular

ceramics from silicone resins with a zeolite surface, Ceramic Eng. Sci. Proceed. 23, 203-210

(2002).

10. Jansen, J. C. et al. Zeolite coatings and their potential use in catalysis, Microporous Mesoporous

Mater. 21, 213-226 (1998); van der Puil, N., Dautzenberg, F. M., van Bekkum, H. & Jansen, J. C.

Preparation and catalytic testing of zeolite coatings on preshaped alumina supports, Microporous

Mesoporous Mater. 27, 95-106 (1999).

11. G. T. P. Mabande, T. Selvam, W. Schwiegeer, M. Hanebuth, R. Dyttmeyer, Herstellung von

gestützen Zeolithschichten, Pat. Appl. DE10304322.5 (2002); Lai, Z. et al. Microstructural

optimization of a zeolite membrane for organic vapor separation, Science 300, 456-460 (2003).

12. Scheffler, F., Schwieger, W., Freude, D., Liu, H., Heyer, W. & Janowski, F. Transformation of

porous glass beads into MFI-type containing beads, Microporous Mesoporous Mater. 55, 181-191

(2002); Katsuki, H. & Furuta, S. Formation of novel ZSM-5/porous mullite composite from

sintered kaolin honeycomb by hydrothermal reaction, J. Am. Ceram. Soc. 83, 1093-1097 (2000).

13. Seijger, G. B. F., Oudshoorn, O. L., Boekhorst, A., van Bekkum, H., van den Bleek, C. M. &

Calis, H. P. A., Selective catalytic reduction of NOx over zeolite-coated structured catalyst

packings, Chem. Eng. Sci. 56, 849-857 (2001); Cybulski, A. & Moulijn, J. A. Structured Catalysts

and Reactors, 1998 (ed. by A. Cybulski and J. Moulijn).

14. Wang, Y., Tang, Y., Dong, A., Wang, X., Ren, N., Shan, W. & Gao, Z. Self-supporting porous

zeolite membranes with sponge-like architecture and zeolitic microtubes, Adv. Mater. 14, 994-997

(2002).

15. Dong, A., Wang, Y., Tang, Y., Ren, N., Zhang, Y., Yue, Y. & Gao, Z. Zeolitic tissue through

wood cell templating, Adv. Mater. 14, 926-929 (2002); Daw, R. Zeolite branch out, Nature 418,

491 (2002); Anderson, M. W., Holmes, S. M., Hanif, N. & Cundy, C. Hierarchical pore structures

through diatom zeolitization, Angew. Chem. Int. Ed. 39, 2707-2710 (2000).



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