Unbiased Reaction Network Exploration of C–C Coupling in Methane Dehydroaromatization Over Mo‐ZSM‐5

ABSTRACT Methane dehydroaromatization (MDA) over Mo‐ZSM‐5 zeolite catalysts is a promising route for the direct conversion of methane into valuable aromatic hydrocarbons. However, catalyst deactivation caused by coke formation remains a major challenge, and the underlying mechanisms are not fully understood. In this study, we applied automated reaction route mapping combined with rate constant matrix contraction (RCMC) to systematically explore reaction networks originating from methane molecules over two plausible active sites, [MoC] 2+ and [Mo 2 C 2 ] 2+ , confined within ZSM‐5 zeolite. Without assuming predefined reaction products, the mapping revealed distinct reaction pathways and energetics for each active site. Over [MoC] 2+ , C 2 H 4 was identified as a key intermediate with a relatively low desorption energy. In contrast, [Mo 2 C 2 ] 2+ facilitated the formation of C 3 and C 4 species with high desorption energies. Importantly, the regeneration of [MoC] 2+ from methane alone was not observed, whereas CO promoted regeneration, consistent with experimental reports of CO‐assisted catalyst stability. These findings provide detailed mechanistic insight into hydrocarbon formation and catalyst deactivation and highlight the utility of automated reaction mapping in rational catalyst design.