Mechanisms and Kinetics of the Dehydrogenation of C6–C8 Cycloalkanes, Cycloalkenes, and Cyclodienes to Aromatics in H-MFI Zeolite Framework

This work employs periodic density functional theory to elucidate dehydrogenation mechanisms of C6–C8 cycloalkanes, cycloalkenes, and cyclodienes into aromatics during methanol-to-olefin (MTO) chemistries in H-MFI zeolites. Aromatic compounds act as co-catalysts that predominantly form ethylene over propylene products and lead to site-blocking polyaromatic compounds; thus, understanding the formation of aromatic compounds during MTO is critical to understanding its selectivity and catalyst stability. Ring dehydrogenation reactions occur via sequential hydride transfer followed by deprotonation. The rate-controlling hydride transfer reactions were investigated with surface-bound protons (Z–H) and alkyls (Z–CnH2n+1) as hydride-accepting species. Hydride transfers via proton-mediated routes occur with intrinsic free energy barriers (623 K) of 215 kJ mol–1 for C6H12, 164 kJ mol–1 for C6H10, and 141 kJ mol–1 for C6H8, whereas methyl-mediated counterparts occur with intrinsic free barriers of 101, 95, and 81 kJ mol–1, respectively. Transition states for hydride transfer reactions prefer channel intersections within MFI networks, and their activation barriers suggest that methyl-mediated routes are favored over proton-mediated counterparts during MTO. Methyl substituents on hydrocarbon rings generally increase activation barriers for hydride transfers that occur proximal to the −CH3, partly because of steric hindrances between the hydride acceptor and ring-bound −CH3. Rapid double-bond isomerization within cyclohexenes and cyclohexadienes allows hydride transfer reactions to occur away from sterically hindering methyl substituents in methylated and dimethylated C6 ring hydrocarbons. The impact of carbocation substitution in hydride-accepting species was explored by contrasting barriers of methyl (Z–CH3), ethyl (Z–C2H5), 2-propyl (Z–C3H7), and tert-butyl (Z–C4H9) surface-bound alkyls. Intrinsic activation barriers decrease with increasing substitution of the alkyl hydride acceptor, consistent with those alkyls forming more stable carbocations. However, when accounting for steric hindrances associated with the co-adsorption of hydrocarbon rings near surface-bound alkyls, apparent free barriers are larger for more-substituted alkyls. Taking these apparent barriers into account, we predict that methyl-mediated hydride transfer reactions are responsible for the aromatization of hydrocarbon rings during MTO, leading to the CH4 formed during MTO reactions as the aromatic pool is enriched.