Abstract

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.

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