(174as) Theoretical Investigations of Lewis Acid-Catalyzed Alkane C-H Activation in Metal-Modified Zeolites
The increasing availability of large shale gas reserves worldwide, has stimulated interest in finding routes for the valorization of C2-C4 alkanes. C-H Activation over metal-modified zeolites such as Ga/H-MFI yields higher selectivities to alkenes and aromatics than those observed over unmodified H-MFI which contains only protons ; In earlier characterization  and computational studies , [GaH]2+ cations were found to be stable under reducing conditions and active for alkane dehydrogenation. In the present study, insights into alkane cracking and dehydrogenation on [GaH]2+, Zn2+ and other Group 13 hydrides exchanged into MFI are developed for the activation of C2-C4 alkanes. A long-range corrected QM/MM scheme was used where the QM region is represented using the dispersion-corrected density functional ÏB97X-D, while the MM region uses CHARMM Force fields. Reported activation energies are computed using a triple-Î¶, split valence basis set: 6-311++G(3df,3pd). Our theoretical results suggest that alkyl-activated pathways are relevant for both butane and propane conversions on [GaH]2+ sites in Ga/H-MFI and Zn2+ sites in Zn/H-MFI and that the mechanistic insights obtained here are of broader relevance to the rational design of other metal-exchanged zeolites for light alkane activation.
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