Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10–15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm3 g−1) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Communications Open Access 31 May 2023
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
Prices may be subject to local taxes which are calculated during checkout
Breck, D. W. Zeolites and Molecular Sieves System (Wiley, 1974).
Vermeiren, W. & Gilson, J-P. Impact of zeolites on the petroleum and petrochemical industry. Top. Catal. 52, 1131–1161 (2009).
Martinez, C. & Corma, A. Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes. Coord. Chem. Rev. 255, 1558–1580 (2011).
Perego, C. & Bosetti, A. Biomass to fuels: The role of zeolite and mesoporous materials. Microporous Mesoporous Mater. 144, 28–39 (2011).
Guisnet, M. & Gilson, J-P. Zeolites for Cleaner Technologies (Imperial College Press, 2002).
Valtchev, V., Majano, G., Mintova, S. & Pérez-Ramírez, J. Tailored crystalline microporous materials by post-synthesis modification. Chem. Soc. Rev. 42, 263–290 (2013).
Kulprathipanja, S. Zeolites in Industrial Separation and Catalysis (Wiley-VCH, 2010).
Chen, N. Y., Degnan, T. F. C. & Smith, M. Molecular Transport and Reaction in Zeolites: Design and Application of Shape Selective Catalysis (John Wiley, 1994).
Jacobs, P. A., Dusselier, M. & Sels, B. F. Will zeolite-based catalysis be as relevant in future biorefineries as in crude oil refineries? Angew. Chem. Int. Ed. 53, 2–8 (2014).
Gilson, J-P., Marie, O., Mintova, S. & Valtchev, V. Zeolites and Ordered Porous Solids, 3rd FEZA School on Zeolites: Fundamentals and Applications (Editorial Universitat Politècnica de València, 2011).
Bein, T. & Mintova, S. Advanced Applications of Zeolites in Zeolites and Ordered Mesoporous Materials: Progress and Prospects Vol. 263 (Elsevier, 2005).
Mintova, S., Olson, N. H. & Bein, T. Electron microscopy reveals the nucleation mechanism of zeolite Y from precursor colloids. Angew. Chem. 38, 3201–3204 (1999).
Yang, S. Y., Navrotsky, A. & Phillips, B. L. An in situ calorimetric study of the synthesis of FAU zeolite. Microporous Mesoporous Mater. 46, 137–151 (2001).
Li, Q. H., Creaser, D. & Sterte, J. An investigation of the nucleation/crystallization kinetics of nanosized colloidal faujasite zeolites. Chem. Mater. 14, 1319–1324 (2002).
Holmberg, B. A., Wang, H., Norbeck, J. M. & Yan, Y. Controlling size and yield of zeolite Y nanocrystals using tetramethylammonium bromide. Microporous Mesoporous Mater. 59, 13–28 (2003).
Larsen, S. C. Nanocrystalline zeolites and zeolite structures: Synthesis, characterization, and applications. J. Phys. Chem. C 111, 18464–18474 (2007).
Tosheva, L. & Valtchev, V. Nanozeolites: Synthesis, crystallization mechanism, and applications. Chem. Mater. 17, 2494–2513 (2005).
Larlus, O., Mintova, S. & Bein, T. Environmental syntheses of nanosized zeolites with high yield and monomodal particle size distribution. Microporous Mesoporous Mater. 96, 405–412 (2006).
Li, Q., Mihailova, B., Creaser, D. & Sterte, J. The nucleation period for crystallization of colloidal TPA-silicalite-1 with varying silica source. Microporous Mesoporous Mater. 40, 53–62 (2000).
Morales-Pacheco, P. et al. Synthesis of FAU(Y)- and MFI(ZSM5)-nanosized crystallites for catalytic cracking of 1,3,5-triisopropylbenzene. Catal. Today 166, 25–38 (2011).
Valtchev, V. P. & Bozhilov, K. N. TEM study of the formation of FAU-type zeolite at room temperature. J. Phys. Chem. B 108, 15587–15598 (2004).
Zhan, B-Z. et al. Control of particle size and surface properties of crystals of NaX zeolite. Chem. Mater. 14, 3636–3642 (2002).
Ng, E-P., Chateigner, D., Bein, T., Valtchev, V. & Mintova, S. Capturing ultrasmall EMT zeolite from template-free systems. Science 335, 70–73 (2012).
Mintova, S., Olson, N. H., Valtchev, V. & Bein, T. Mechanism of zeolite A nanocrystal growth from colloids at room temperature. Science 283, 958–960 (1999).
Barrer, R. M. Hydrothermal Chemistry of Zeolites (Academic Press, 1982).
Engelhardt, G. & Michel, D. High Resolution Solid State NMR of Silicates and Zeolites (Wiley, 1987).
Treacy, M. M. J., Vaughan, D. E. W., Strohmaier, K. G. & Newsam, J. M. Intergrowth segregation in FAU-EMT zeolite materials. Proc. R. Soc. Lond. A 452, 813–840 (1996).
Khaleel, M., Wagner, A. J., Mkhoyan, A. & Tsapatsis, M. On the rotational intergrowth of hierarchical FAU/EMT zeolites. Angew. Chem. Int. Ed. 53, 9456–9461 (2014).
Chateigner, D. Combined Analysis (Wiley-ISTE, 2010).
Lutterotti, L., Matthies, S. & Wenk, H-R. in Textures of Materials (ed Szpunar, J. A.) (NRC Research Press, 2002).
Chal, R., Gerardin, C., Bulut, M. & van Donk, S. Overview and industrial assessment of synthesis strategies towards zeolites with mesopores. ChemCatChem 3, 67–81 (2011).
Verboekend, D. et al. Mesoporous ZSM-22 zeolite obtained by desilication: Peculiarities associated with crystal morphology and aluminium distribution. Catal. Sci. Technol. 1, 3408–3416 (2011).
Martens, J. A. et al. Hydroisomerization of emerging renewable hydrocarbons using hierarchical Pt/H-ZSM-22 catalyst. ChemSusChem 6, 421–425 (2013).
Rajagopalan, K., Peters, A. W. & Edwards, G. C. Influence of zeolite particle size on selectivity during fluid catalytic cracking. Appl. Catal. 23, 69–80 (1986).
Derouane, E. G., Gilson, J-P., Gabelica, Z., Mousty-Desbuquoit, C. & Verbist, J. Concerning the aluminum distribution gradient in ZSM-5 zeolites. J. Catal. 71, 447–448 (1981).
Gilson, J-P. & Derouane, E. G. On the external and intracrystalline surface catalytic activity of pentasil zeolites. J. Catal. 88, 538–541 (1984).
Corma, A. et al. 2,6-di-tert-butyl-pyridine as a probe molecule to measure external acidity of zeolites. J. Catal. 179, 451–458 (1998).
The financial support from the Region of Lower Normandy and the MEET INTEREG EC and MicroGreen (ANR-12-IS08-01) projects is acknowledged.
The authors declare no competing financial interests.
About this article
Cite this article
Awala, H., Gilson, JP., Retoux, R. et al. Template-free nanosized faujasite-type zeolites. Nature Mater 14, 447–451 (2015). https://doi.org/10.1038/nmat4173
This article is cited by
Nature Catalysis (2023)
Nature Communications (2023)
DTAB Mediated Post Modification of Zeolite H-BEA, Its Characterization and Catalytic Application for n-Butyl Levulinate Synthesis
Catalysis Surveys from Asia (2023)
Journal of Cluster Science (2023)
Nature Synthesis (2022)