Insights into the reaction mechanism of n-hexane dehydroaromatization to benzene over gallium embedded HZSM-5: effect of H2 incorporated on active sites

The catalytic dehydroaromatization of alkanes to aromatics has attracted considerable attention from the scientific community, because it can be used for the upgrading of low-cost alkanes into high added-value aromatics, such as benzene, toluene, and xylene (BTX). In this context, we report the reaction mechanism of n-hexane dehydroaromatization to benzene over two different reduced gallium species embedded in HZSM-5, including univalent Ga+ embedded in HZSM-5 (Ga/HZSM-5) and dihydrido gallium complex (GaH2+) embedded in HZSM-5 (GaH2/HZSM-5) by using the M06-2X/6-31G(d,p) level of calculation. The reaction proceeds by following two main steps: (i) the dehydrogenation of hexane to haxa-1,3,5-triene; (ii) the dehydroaromatization of haxa-1,3,5-triene to benzene. For the univalent Ga+ embedded in HZSM-5, the first step of the hexane dehydrogenation is considered to be the rate-determining step, which requires a high activation energy of 76.6 kcal mol−1. In strong contrast to this, in the case of the GaH2/HZSM-5 catalyst the rate determining step is found to be the second hydrogen abstraction from n-hexane with a lower activation barrier of 11.1 kcal mol−1. The reaction is therefore preferentially taking place over the GaH2/HZSM-5 catalyst. These observations clearly confirm the existence of a dihydrido gallium complex (GaH2+) as one of the most active species for the dehydroaromatization of alkanes and it is obtained in the presence of hydrogen in the catalytic system. This example opens up perspectives for a better understanding of the effect of active species on the catalytic reaction.