Co-Feeding CO₂ for Methylfuran Aromatization over Bifunctional Zeolite-Supported ZnMoO₄

Aromatization of biofuran offers promising approaches for sustainable biochemical production. However, this process is often hampered by low yields and severe coking on traditional zeolite catalysts. Herein, we report co-feeding CO₂ for 2-methylfuran (MF) aromatization (CCMA) over bifunctional ZSM-5 supported ZnMoO₄. This bifunctional catalyst can achieve both MF and CO₂ conversions of >97 %, generating >85 % carbon yield of target arenes and CO with negligible alkenes (0.05 %). Meanwhile, coke formation is remarkably suppressed from 22.3 % to 8.6 %. ZnMoO₄/ZSM-5 is capable of selectively manipulating the reaction intermediates and pathways of the CCMA reactions, favoring the cyclopentenones- and alkenes-based dehydro-aromatization rather than the benzofurans-based pathway. This finding challenges the prevailing understanding that MF aromatization follows a hydrocarbon pool mechanism. Moreover, the abundant surface oxygen vacancies of ZnMoO₄ facilitate the adsorption of CO₂ and its subsequent reaction with coke. These insights into reaction mechanism and catalyst design for co-conversion of CO₂ and biofuran can offer guidelines for process intensification in biomass utilization with a carbon-negative manner.