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- Choi, Minkee, et al.
(författare)
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Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts
- 2009
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Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 461:7261, s. 246-249
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Tidskriftsartikel (refereegranskat)abstract
- Zeolites-microporous crystalline aluminosilicates-are widely used in petrochemistry and fine-chemical synthesis(1-3) because strong acid sites within their uniform micropores enable size- and shape-selective catalysis. But the very presence of the micropores, with aperture diameters below 1 nm, often goes hand-in-hand with diffusion limitations(3-5) that adversely affect catalytic activity. The problem can be overcome by reducing the thickness of the zeolite crystals, which reduces diffusion path lengths and thus improves molecular diffusion(4,5). This has been realized by synthesizing zeolite nanocrystals(6), by exfoliating layered zeolites(7-9), and by introducing mesopores in the microporous material through templating strategies(10-17) or demetallation processes(18-22). But except for the exfoliation, none of these strategies has produced 'ultrathin' zeolites with thicknesses below 5 nm. Here we show that appropriately designed bifunctional surfactants can direct the formation of zeolite structures on themesoporous and microporous length scales simultaneously and thus yield MFI (ZSM-5, one of the most important catalysts in the petrochemical industry) zeolite nanosheets that are only 2 nm thick, which corresponds to the b-axis dimension of a single MFI unit cell. The large number of acid sites on the external surface of these zeolites renders them highly active for the catalytic conversion of large organic molecules, and the reduced crystal thickness facilitates diffusion and thereby dramatically suppresses catalyst deactivation through coke deposition during methanol-to-gasoline conversion. We expect that our synthesis approach could be applied to other zeolites to improve their performance in a range of important catalytic applications.
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| 2. |
- Na, Kyungsu, et al.
(författare)
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Pillared MFI Zeolite Nanosheets of a Single-Unit-Cell Thickness
- 2010
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 132:12, s. 4169-4177
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Tidskriftsartikel (refereegranskat)abstract
- Zeolite MFI nanosheets of 2-nm thickness have been hydrothermally synthesized via cooperative assembly between silica and an organic surfactant, which is functionalized with a diquaternary ammonium group. The zeolite nanosheets have been further assembled into their ordered multilamellar mesostructure through hydrophobic interactions between the surfactant tails located outside the zeolite nanosheet. This assembly process involves successive transformations from an initially hexagonal mesophase to a multilamellar mesophase without crystallinity and then to a lamellar mesophase with a crystalline zeolite framework. The mesopore volume in the interlamellar space could be retained by supporting the zeolite nanosheets with silica pillars, as in pillared clays, even after surfactant removal by calcination. The mesopore diameters could be controlled according to the surfactant tail lengths. Due to the interlamellar structural coherence, the hierarchically mesoporous/microporous zeolite could exhibit small-angle X-ray diffraction peaks up to the fourth-order reflections corresponding to the interlayer distance. In addition, an Ar adsorption analysis and transmission electron microscopic investigation indicated that the pillars were highly likely to be built with an MFI structure. The present approach using a zeolite structure-directing functional group contained in a surfactant would be suitable for the synthesis of other related nanomorphous zeolites in the future.
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