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Despite their widespread use, the mechanisms governing the synthesis of zeolite catalysts are still poorly understood. A notable example of this problem is the uncertainty surrounding the influence of synthesis conditions on the placement of Al atoms in the zeolite framework, which determines the active sites available for catalytic species. In this work, the role of the cis to trans isomer ratio of the OSDA N,N-dimethyl-3-5-dimethylpiperidinium on the energetics of 26 distinct Al pair distributions in SSZ-39 is examined both in the presence and absence of Na using density functional theory calculations. The initial orientation of the OSDA was found to have a significant impact on the final energies present, necessitating the screening of a large number of initial orientations with force field calculations and single point DFT calculations. Ground state energies were found to vary significantly with the ratio of cis to trans OSDAs with a Boltzmann distribution revealing the most likely Al pair distributions shift from sharing the same 8 membered rings to sharing the same double 6-membered rings to having no shared subunits as one increases the amount of cis OSDA present within the framework. The presence of Na was found to favor Al pair distributions where both Als occupied the same 6-membered ring. When an implicit solvent model was used to evaluate ground state energies the ideal Na sites shifted from 6-membered rings to empty SSZ-39 cages while OSDA positions and orientations remained largely the same. To provide insight on how kinetic factors may influence Al distributions, formation energies we calculated for connected double 6-membered rings. These formation energies revealed a preference for Al pairs to occupy the same 4-membered ring, which indicates kinetic and thermodynamic control may lead to different Al distributions in SSZ-39.
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This content will become publicly available on March 6, 2026
Quantifying how the cis / trans ratio of N , N -dimethyl-3,5-dimethylpiperidinium hydroxide impacts the growth kinetics, composition and local structure of SSZ-39
This work integrates experiments and computational methods to quantify how the cis/trans ratio of the OSDA used in SSZ-39 synthesis impacts the crystallization kinetics, material properties, and final product composition. The crystallization kinetics increase by 30% when increasing the trans isomer content from 14% to 80%. Per prior work, in all cases based on the synthesis gel composition and product yield aluminum is the limiting reagent, and the absence of any amorphous material detected in the time resolved PXRD studies leads us to conclude that FAU dissolution is the rate limiting step in the formation of SSZ-39 in this synthesis protocol. The TGA and NMR results suggest that the trans isomer of OSDA is selectively incorporated into the product. The NMR binding studies, and corresponding DFT-based results show that the trans isomer binds to FAU more strongly than the cis isomer, providing one possible explanation for this enhancement in kinetics and preferential uptake of the trans isomer. The EDS analysis indicates that the Si/Al ratios are between 7.7 and 8.6 at low and high trans OSDA content, indicating zeolite composition is mildly sensitive to the trans isomer content. EDS results show this decrease in aluminum content leads to a corresponding decrease in sodium uptake. DFT-based calculations confirm OSDA–sodium interactions cannot explain any decrease in sodium uptake, reinforcing lower aluminum content as the cause of lower sodium uptake. Preliminary cobalt titration experiments show a surprisingly low cobalt uptake but also show a clear dependence of the cobalt uptake on the solution pH.
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- Award ID(s):
- 2035280
- PAR ID:
- 10595445
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- RSC Advances
- Volume:
- 15
- Issue:
- 10
- ISSN:
- 2046-2069
- Page Range / eLocation ID:
- 7962 to 7972
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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