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Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations

(2020) ACS CATALYSIS. 10(15). p.8904-8915
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Abstract
The methanol-to-hydrocarbon process is known to proceed autocatalytically in H-ZSM-5 after an induction period where framework methoxy species are formed. In this work, we provide mechanistic insight into the framework methylation within H-ZSM-5 at high methanol loadings and varying acid site densities by means of first-principles molecular dynamics simulations. The molecular dynamics simulations show that stable methanol clusters form in the zeolite pores, and these clusters commonly deprotonate the active site; however, the cluster size is dependent on the temperature and acid site density. Enhanced sampling molecular dynamics simulations give evidence that the barrier for methanol conversion is significantly affected by the neighborhood of an additional acid site, suggesting that cooperative effects influence methanol clustering and reactivity. The insights obtained are important steps in optimizing the catalyst and engineering the induction period of the methanol-to-hydrocarbon process.
Keywords
zeolite, acidity, methanol, methylation, methanol-to-hydrocarbons, metadynamics, TO-HYDROCARBONS REACTION, DIMETHYL ETHER, H-Y, CONVERSION, ZEOLITES, ZSM-5, REACTIVITY, PROTON, NMR, METHOXYLATION

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MLA
Nastase, Stefan A. F., et al. “Mechanistic Insight into the Framework Methylation of H-ZSM-5 for Varying Methanol Loadings and Si/Al Ratios Using First-Principles Molecular Dynamics Simulations.” ACS CATALYSIS, vol. 10, no. 15, 2020, pp. 8904–15, doi:10.1021/acscatal.0c01454.
APA
Nastase, S. A. F., Cnudde, P., Vanduyfhuys, L., De Wispelaere, K., Van Speybroeck, V., Catlow, C. R. A., & Logsdail, A. J. (2020). Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations. ACS CATALYSIS, 10(15), 8904–8915. https://doi.org/10.1021/acscatal.0c01454
Chicago author-date
Nastase, Stefan A. F., Pieter Cnudde, Louis Vanduyfhuys, Kristof De Wispelaere, Veronique Van Speybroeck, C. Richard A. Catlow, and Andrew J. Logsdail. 2020. “Mechanistic Insight into the Framework Methylation of H-ZSM-5 for Varying Methanol Loadings and Si/Al Ratios Using First-Principles Molecular Dynamics Simulations.” ACS CATALYSIS 10 (15): 8904–15. https://doi.org/10.1021/acscatal.0c01454.
Chicago author-date (all authors)
Nastase, Stefan A. F., Pieter Cnudde, Louis Vanduyfhuys, Kristof De Wispelaere, Veronique Van Speybroeck, C. Richard A. Catlow, and Andrew J. Logsdail. 2020. “Mechanistic Insight into the Framework Methylation of H-ZSM-5 for Varying Methanol Loadings and Si/Al Ratios Using First-Principles Molecular Dynamics Simulations.” ACS CATALYSIS 10 (15): 8904–8915. doi:10.1021/acscatal.0c01454.
Vancouver
1.
Nastase SAF, Cnudde P, Vanduyfhuys L, De Wispelaere K, Van Speybroeck V, Catlow CRA, et al. Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations. ACS CATALYSIS. 2020;10(15):8904–15.
IEEE
[1]
S. A. F. Nastase et al., “Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations,” ACS CATALYSIS, vol. 10, no. 15, pp. 8904–8915, 2020.
@article{8678618,
  abstract     = {The methanol-to-hydrocarbon process is known to proceed autocatalytically in H-ZSM-5 after an induction period where framework methoxy species are formed. In this work, we provide mechanistic insight into the framework methylation within H-ZSM-5 at high methanol loadings and varying acid site densities by means of first-principles molecular dynamics simulations. The molecular dynamics simulations show that stable methanol clusters form in the zeolite pores, and these clusters commonly deprotonate the active site; however, the cluster size is dependent on the temperature and acid site density. Enhanced sampling molecular dynamics simulations give evidence that the barrier for methanol conversion is significantly affected by the neighborhood of an additional acid site, suggesting that cooperative effects influence methanol clustering and reactivity. The insights obtained are important steps in optimizing the catalyst and engineering the induction period of the methanol-to-hydrocarbon process.},
  author       = {Nastase, Stefan A. F. and Cnudde, Pieter and Vanduyfhuys, Louis and De Wispelaere, Kristof and Van Speybroeck, Veronique and Catlow, C. Richard A. and Logsdail, Andrew J.},
  issn         = {2155-5435},
  journal      = {ACS CATALYSIS},
  keywords     = {zeolite,acidity,methanol,methylation,methanol-to-hydrocarbons,metadynamics,TO-HYDROCARBONS REACTION,DIMETHYL ETHER,H-Y,CONVERSION,ZEOLITES,ZSM-5,REACTIVITY,PROTON,NMR,METHOXYLATION},
  language     = {eng},
  number       = {15},
  pages        = {8904--8915},
  title        = {Mechanistic insight into the framework methylation of H-ZSM-5 for varying methanol loadings and Si/Al ratios using first-principles molecular dynamics simulations},
  url          = {http://dx.doi.org/10.1021/acscatal.0c01454},
  volume       = {10},
  year         = {2020},
}

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