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Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites

(2015) JOURNAL OF PHYSICAL CHEMISTRY C. 119(41). p.23721-23734
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Abstract
The diffusion of olefins through 8-ring solid acid microporous zeolites is investigated using molecular dynamics simulations techniques and using a newly developed flexible force field. Within the context of the methanol-to-olefin (MTO) process and the observed product distribution, knowledge of the diffusion paths is essential to obtain molecular level control over the process conditions. Eight-ring zeotype materials are favorably used for the MTO process as they give a selective product distribution toward low-carbon olefins. To investigate how composition, acidity, and flexibility influence the diffusion paths of ethene and propene, a series of isostructural aluminosilicates (zeolites) and silicoaluminophosphates (AlPOs and SAPOs) are investigated with and without randomly distributed acidic sites. Distinct variations in diffusion of ethene are observed in terms of temperature, composition, acidity, and topology (AEI, CHA, AFX). In general, diffusion of ethene is an activated process for which free energy barriers for individual rings may be determined. We observe ring-dependent diffusion behavior which cannot be described solely in terms of the composition and topology of the rings. A new descriptor had to be introduced, namely, the accessible window area (AWA), inspired by implicit solvation models of proteins and small molecules. The AWA may be determined throughout the molecular dynamics trajectories and correlates well with the number of ring crossings at the molecular level and the free energy barriers for ring crossings from one cage to the other. The overall observed diffusivity is determined by molecular characteristics of individual rings for which AWA is a proper descriptor. Temperature-induced changes in framework dynamics and diffusivity may be captured by following the new descriptor throughout the simulations.
Keywords
MOLECULAR-DYNAMICS SIMULATIONS, NEGATIVE THERMAL-EXPANSION, NMR SELF-DIFFUSION, HIGH-SILICA DDR, FRAMEWORK FLEXIBILITY, REACTION-MECHANISM, INTERATOMIC POTENTIALS, HYDROCARBON FORMATION, MODELING ADSORPTION, LTA STRUCTURES

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Citation

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MLA
Ghysels, An et al. “Shape-selective Diffusion of Olefins in 8-ring Solid Acid Microporous Zeolites.” JOURNAL OF PHYSICAL CHEMISTRY C 119.41 (2015): 23721–23734. Print.
APA
Ghysels, A., Moors, S., Hemelsoet, K., De Wispelaere, K., Waroquier, M., Sastre, G., & Van Speybroeck, V. (2015). Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites. JOURNAL OF PHYSICAL CHEMISTRY C, 119(41), 23721–23734.
Chicago author-date
Ghysels, An, Samuel Moors, Karen Hemelsoet, Kristof De Wispelaere, Michel Waroquier, German Sastre, and Veronique Van Speybroeck. 2015. “Shape-selective Diffusion of Olefins in 8-ring Solid Acid Microporous Zeolites.” Journal of Physical Chemistry C 119 (41): 23721–23734.
Chicago author-date (all authors)
Ghysels, An, Samuel Moors, Karen Hemelsoet, Kristof De Wispelaere, Michel Waroquier, German Sastre, and Veronique Van Speybroeck. 2015. “Shape-selective Diffusion of Olefins in 8-ring Solid Acid Microporous Zeolites.” Journal of Physical Chemistry C 119 (41): 23721–23734.
Vancouver
1.
Ghysels A, Moors S, Hemelsoet K, De Wispelaere K, Waroquier M, Sastre G, et al. Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites. JOURNAL OF PHYSICAL CHEMISTRY C. 2015;119(41):23721–34.
IEEE
[1]
A. Ghysels et al., “Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites,” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 119, no. 41, pp. 23721–23734, 2015.
@article{6977088,
  abstract     = {The diffusion of olefins through 8-ring solid acid microporous zeolites is investigated using molecular dynamics simulations techniques and using a newly developed flexible force field. Within the context of the methanol-to-olefin (MTO) process and the observed product distribution, knowledge of the diffusion paths is essential to obtain molecular level control over the process conditions. Eight-ring zeotype materials are favorably used for the MTO process as they give a selective product distribution toward low-carbon olefins. To investigate how composition, acidity, and flexibility influence the diffusion paths of ethene and propene, a series of isostructural aluminosilicates (zeolites) and silicoaluminophosphates (AlPOs and SAPOs) are investigated with and without randomly distributed acidic sites. Distinct variations in diffusion of ethene are observed in terms of temperature, composition, acidity, and topology (AEI, CHA, AFX). In general, diffusion of ethene is an activated process for which free energy barriers for individual rings may be determined. We observe ring-dependent diffusion behavior which cannot be described solely in terms of the composition and topology of the rings. A new descriptor had to be introduced, namely, the accessible window area (AWA), inspired by implicit solvation models of proteins and small molecules. The AWA may be determined throughout the molecular dynamics trajectories and correlates well with the number of ring crossings at the molecular level and the free energy barriers for ring crossings from one cage to the other. The overall observed diffusivity is determined by molecular characteristics of individual rings for which AWA is a proper descriptor. Temperature-induced changes in framework dynamics and diffusivity may be captured by following the new descriptor throughout the simulations.},
  author       = {Ghysels, An and Moors, Samuel and Hemelsoet, Karen and De Wispelaere, Kristof and Waroquier, Michel and Sastre, German and Van Speybroeck, Veronique},
  issn         = {1932-7447},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY C},
  keywords     = {MOLECULAR-DYNAMICS SIMULATIONS,NEGATIVE THERMAL-EXPANSION,NMR SELF-DIFFUSION,HIGH-SILICA DDR,FRAMEWORK FLEXIBILITY,REACTION-MECHANISM,INTERATOMIC POTENTIALS,HYDROCARBON FORMATION,MODELING ADSORPTION,LTA STRUCTURES},
  language     = {eng},
  number       = {41},
  pages        = {23721--23734},
  title        = {Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites},
  url          = {http://dx.doi.org/10.1021/acs.jpcc.5b06010},
  volume       = {119},
  year         = {2015},
}

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