Ab initio enhanced sampling kinetic study on MTO ethene methylation reaction

S. Bailleul, K. Dedecker, P. Cnudde, L. Vanduyfhuys, M. Waroquier, V. Van Speybroeck
Journal of Catalysis
388, 38-51


The methylation reaction of ethene with methanol over the Brønsted acidic ZSM-5 catalyst is one of theprototype reactions within zeolite catalysis for which experimental kinetic data is available. It is one ofthe premier reactions within the methanol-to-olefins process and has been the subject of extensive the-oretical testing to predict the reaction rates. Herein, we apply, for the first time, first principle moleculardynamics methods to determine the intrinsic reaction kinetics taking into account the full configurationalentropy. As chemical reactions are rare events, enhanced sampling methods are necessary to obtain suf-ficient sampling of the configurational space at the activated region. A plethora of methods is availablewhich depend on specific choices like the selection of collective variables along which the dynamics isenhanced. Herein, a thorough first principle molecular dynamics study is presented to determine thereaction kinetics via various enhanced MD techniques on an exemplary reaction within zeolite catalysisfor which reference theoretical and experimental data are available.

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