| 1. |
- Dai, Heng, et al.
(författare)
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Finned zeolite catalysts
- 2020
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Ingår i: Nature Materials. - : Springer Science and Business Media LLC. - 1476-1122 .- 1476-4660. ; 19:10, s. 1074-1080
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Tidskriftsartikel (refereegranskat)abstract
- Nanosized zeolites enable better catalytic performance; however, their synthesis is non-trivial. Here, a simple treatment is presented that enables the growth of nanosized fins on zeolites that act as pseudo-nanoparticles, reducing deactivation rates for methanol-to-hydrocarbon catalysis. There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.
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| 2. |
- Qi, Liang, et al.
(författare)
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Dehydrogenation of Propane and n-Butane Catalyzed by Isolated PtZn4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets
- 2022
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:18, s. 11177-11189
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Tidskriftsartikel (refereegranskat)abstract
- Propene and 1,3-butadiene are important building-block chemicals that can be produced by dehydrogenation of propane and butane on Pt catalysts. A challenge is to develop highly active and selective catalysts that are resistant to deactivation by Pt sintering and coke formation. We have recently shown (Qi , J. Am. Chem. Soc. 2021, 143, 21364-21378) that these objectives can be met for propane dehydrogenation (PDH) using atomically dispersed Pt anchored to neighboring SiOZn-OH groups bonded to the framework of dealuminated zeolite BEA. In the present study, we demonstrate that significantly superior performance can be achieved using self-pillared pentasil (SPP) zeolite nanosheets as supports. Following catalyst reduction in H-2, atomic resolution, scanning transmission electron microscopy (STEM), and X-ray absorption spectroscopy (XAS) indicate that Pt is stabilized in structures well approximated as ( Si-O-Zn)(4-5)Pt. These species are highly active, selective, and stable for PDH to give propene and for n-butane dehydrogenation (BDH) to give 1,3-butadiene. No catalyst deactivation was observed after 12 days of time on stream, and the selectivity remained at nearly 100% for PDH conducted at 823 K and a weight hourly space velocity (WHSV) of 1350 h(-1). The apparent rate coefficient for PDH on this catalyst is significantly higher than that reported previously for Pt-containing catalysts. For BDH at 823 K and a WHSV of 3560 h(-1), the selectivity to butene isomers and 1,3-butadiene is 98.9%, and the selectivity to 1,3-butadiene is 45%. We propose that the high catalyst stability observed during PDH and BDH is a consequence of a large fraction of the Pt-containing centers being located on the external surface of the zeolite nanosheets, where nascent coke precursors can desorb before condensing to form coke.
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| 3. |
- Zhang, Xueyi, et al.
(författare)
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Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching
- 2012
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 336:6089, s. 1684-1687
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Tidskriftsartikel (refereegranskat)abstract
- Hierarchical zeolites are a class of microporous catalysts and adsorbents that also contain mesopores, which allow for fas transport of bulky molecules and thereby enable improved performance in petrochemical and biomass processing. We used repetitive branching during one-step hydrothermal crystal growth to synthesize a new hierarchical zeolite made of orthogonally connected microporous nanosheets. The nanosheets are 2 nanometers thick and contain a network of 0.5-nanometer micropores. The house-of-cards arrangement of the nanosheets creates a permanent network of 2- to 7-nanometer mesopores, which, along with the high external surface area and reduced micropore diffusion length, account for higher reaction rates for bulky molecules relative to those of other mesoporous and conventional MFI zeolites.
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