Co-Feeding CO for Methylfuran Aromatization over Bifunctional Zeolite-Supported ZnMoO.

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 CO for 2-methylfuran (MF) aromatization (CCMA) over bifunctional ZSM-5 supported ZnMoO. This bifunctional catalyst can achieve both MF and CO 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 %. ZnMoO/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 ZnMoO facilitate the adsorption of CO and its subsequent reaction with coke. These insights into reaction mechanism and catalyst design for co-conversion of CO and biofuran can offer guidelines for process intensification in biomass utilization with a carbon-negative manner.