Mo/ZSM-5 is one of the most studied and efficient catalysts for the dehydroaromatization of methane (MDA), but the mechanism of its operation remains controversial. Here, we combine an ab initio thermodynamic analysis with a comprehensive mechanistic density functional theory study to address Mo-speciation in the zeolite and identify the active sites under the reaction conditions. We show that the exposure of Mo/ZSM-5 to the MDA conditions yields a range of reduced sites including mono- and binuclear Mo-oxo and Mo-carbide complexes. These sites can catalyze the MDA reaction via two alternative reaction channels, namely, the C-C coupling (ethylene) and the hydrocarbon-pool propagation mechanisms. Our calculations point toward the binuclear Mo-carbide species operating through the hydrocarbon-pool mechanism to be the most catalytically potent species. Although all other Mo sites in the activated catalyst can promote C-H activation in methane, they fail to provide a successful path to the desirable low-molecular-weight products.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was financially supported by NWO veni grant (no. 016.Veni.172.034). NWO surfsara is acknowledged for providing access to the supercomputer facilities. Partial support from the Ministry of education and Science of the Russian Federation (Project 11.1706.2017/4.6) is acknowledged.