Synthesis of a germanosilicate zeolite HPM-12 using a short imidazolium-based dication: structure-direction by charge-to-charge distance matching

Lü, Peng; Gómez‐Hortigüela, Luis; Gao, Zihao; Camblor, Miguel Á.

doi:10.1039/c9dt04089g

Cited by 12 publications

(10 citation statements)

References 33 publications

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“…A decade ago, an OSDA spanning two cages through a 10membered-ring (MR) window was considered "most unusual (and energy-intensive)", 21 although more recent work found a few such instances in STW, 2,11 PTY, 22 and *UOE. 23 However, to the best of our knowledge, our current report is the first case of a three aromatic ring OSDA that directs the crystallization to zeolite STW and, further, it is also the first case of an OSDA crossing two 10MR windows to be located in three different cavities. This kind of OSDA and its packing in the chiral STW channel could provide a new vision to further explore the synthesis of chiral zeolites.…”

Section: Introductionmentioning

confidence: 61%

“…Interestingly, our dication spans three cavities with the benzene ring occupying individually a central cavity and the imidazolium rings sharing the adjacent cavities with imidazolium rings of adjacent dications, as suggested by molecular simulations and confirmed by Rietveld refinement. A decade ago, an OSDA spanning two cages through a 10-membered-ring (MR) window was considered “most unusual (and energy-intensive)”, although more recent work found a few such instances in STW , , PTY , and * UOE . However, to the best of our knowledge, our current report is the first case of a three aromatic ring OSDA that directs the crystallization to zeolite STW and, further, it is also the first case of an OSDA crossing two 10MR windows to be located in three different cavities.…”

Section: Introductionmentioning

confidence: 99%

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Dication Containing Three Aromatic Ring Structure-Directs toward a Chiral Zeolite, Spans Three Cavities, and Effectively Traps Water

et al. 2022

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The chiral zeolite STW has been synthesized using a large dication containing three aromatic rings (two imidazolium moieties plus a benzene one). The integrity of the occluded organics is proven by 1 H and 13 C liquid NMR of the zeolite dissolved in HF/D 2 O. Molecular simulations strongly suggest that each aromatic ring is located in a different cavity so that each dication crosses two medium pore 10-membered-ring (MR) windows. This is confirmed by Rietveld refinement against synchrotron powder X-ray diffraction data, which suggests that there is also trapped water in the cavities, explaining a significant excess of H found in this material. The presence of water is very soundly confirmed by Fourier-transform infrared experiments, which also show that this water cannot leave the zeolite even after heating at 180 °C under vacuum. Molecular simulations allow us to conclude that this is due to the blockage of the 10 and 8MR windows by the occluded organics. The peculiar situation of an organic structure-directing agent spanning three cavities has important implications for the structure-direction concept that are briefly discussed. Several chiral derivatives of this dication have also been studied, and their possibility to enantioselectively direct the crystallization of STW has been analyzed.

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Section: Introductionmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Dication Containing Three Aromatic Ring Structure-Directs toward a Chiral Zeolite, Spans Three Cavities, and Effectively Traps Water

et al. 2022

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“… [9] For the HF dissolution experiment of the as‐made zeolites, the method was reported in a previous work. [52] For the PXRD data collection with a cover of plastic film (Figure S5), the details were reported previously. [20] …”

Section: Methodsmentioning

confidence: 99%

“…Solid state MAS NMR spectra ( 13 C, 19 F, and 29 Si) were carried on a Bruker AV‐400‐WB equipment and the details have been given elsewhere [9] . For the HF dissolution experiment of the as‐made zeolites, the method was reported in a previous work [52] . For the PXRD data collection with a cover of plastic film (Figure S5), the details were reported previously [20] …”

Section: Methodsmentioning

confidence: 99%

Synthesis of Extra‐Large Pore, Large Pore and Medium Pore Zeolites Using a Small Imidazolium Cation as the Organic Structure‐Directing Agent

Gao

Balestra

et al. 2021

Chemistry A European J

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One common strategy in the search for new zeolites is the use of organic structure‐directing agents (OSDA). Typically, one seeks to achieve a high specificity in the structure‐directing effect of the OSDA. This study shows, however, that an OSDA lacking strong specificity towards any particular zeolite may provide opportunities for discovery when other synthesis parameters are systematically screened. Thus, 1‐methyl‐2‐ethyl‐3‐n‐propylimidazolium has allowed to crystallize the new large/medium pore zeolite HPM‐16 as well as the recently reported extra‐large pore ‐SYT and the medium/small pore and chiral STW. The sophisticated OSDA originally affording ‐SYT and the new simple OSDA have very little in common, both in terms of size, shape and flexibility, while both may still direct the synthesis of the same zeolite. In fact, molecular simulations show that the new OSDA is located in three different positions of the ‐SYT structure, including the discrete 8MR where the original organic could not fit.

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“…However, it appears that for polymethylene chains with less than five carbons and with similar terminal groups in terms of steric hindrance in (Si,Al) media, small and medium pore zeolites were discovered. The short imidazolium based dication, 3,3'-(propane-1,3diyl)bis(1,2-dimethyl-1H -imidazol-3-ium) with a shorter propyl linking chain leads to HPM-12 [9], a disordered silicogermanate of topology *UOE [10]. The addition of a carbon in the alkyl chain, (3,3'-(butane-1,4-diyl)bis(1,2-dimethyl-1H -imidazol-3-ium) leads to STW zeolites in pure silica and (Si,Ge) media [11].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of BEC-type germanosilicates with asymmetric diquaternary ammonium salts

Isaac

Paillaud

Daou

et al. 2021

Microporous and Mesoporous Materials

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This paper deals with the synthesis of germanosilicate zeolites using asymmetric diquaternary ammonium salts as organic structure-directing agents (OSDA). Seven pyrrolidinium and piperidinium derivatives were chosen, with different carbon chain lengths and different terminal groups linked to the nitrogen atoms. For each OSDA, the syntheses were performed with four different gel compositions, i.e. in fluoride or hydroxide media both in concentrated or diluted conditions. The products were identified using powder X-ray diffraction data (PXRD). The integrity of the structure-directing agents were verified using 13 C liquid and solid-state NMR spectroscopy and thermogravimetric analyses. For one sample, the Rietveld method allowed us to localize the OSDA inside the pore and the fluoride ions inside the d4r composite building unit but, also inside the main 12-ring channels as proved by 19 F solid-state NMR spectroscopy.

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Synthesis of a germanosilicate zeolite HPM-12 using a short imidazolium-based dication: structure-direction by charge-to-charge distance matching

Abstract: A short dication selectively directing the crystallization of zeolite HPM-12 (*UOE) adopts an unstable conformation in the zeolite.

Cited by 12 publications

References 33 publications

Dication Containing Three Aromatic Ring Structure-Directs toward a Chiral Zeolite, Spans Three Cavities, and Effectively Traps Water

Dication Containing Three Aromatic Ring Structure-Directs toward a Chiral Zeolite, Spans Three Cavities, and Effectively Traps Water

Synthesis of Extra‐Large Pore, Large Pore and Medium Pore Zeolites Using a Small Imidazolium Cation as the Organic Structure‐Directing Agent

Synthesis of BEC-type germanosilicates with asymmetric diquaternary ammonium salts

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