Theoretical study on the dehydrogenation reaction of alkanes catalyzed by zeolites containing nonframework gallium species

The dehydrogenation reaction of light alkanes in gallium-containing zeolites was studied by using density functional theory (DFT) and a nonframework gallium species in the dihydridegallium ion form. Two different mechanisms were considered: a 3-step mechanism and a 1-step concerted mechanism. The reactions occurring through the 3-step mechanism showed smaller activation barriers than the ones following the concerted mechanism. However, the energy barrier for the 3-step mechanism seems to be more influenced by the size and type (linear or branched) of the hydrocarbon chain and demands major conformational rearrangement, which could be hampered by the zeolite framework, especially for larger and/or branched hydrocarbons. On the other hand, the concerted mechanism seems to be much less dependent on the substrates geometry. Therefore, the concerted mechanism could be preferential when dealing with larger and/or branched alkanes.