Investigation of Methane Aromatization Over Mo/ZSM-5 Catalysts with Operando Spectroscopy and DFT Calculations

This investigation represents the first operando molecular spectroscopic study of methane conversion to benzene over supported Mo/ZSM-5 catalysts. The study determines the molecular structures of supported Mo species under different environments and the nature of surface carbon reaction intermediates. Additional molecular structural and reaction mechanistic insights are provided from complementary DFT calculations. The supported Mo phase is present as hydrated Mo8O24 species under ambient conditions, isolated dioxo surface MoO4 species upon dehydration and reduced amorphous MoCx or MoOxCy species during methane activation to benzene.