A Synergistic C ₂₊ Alcohols/Olefins‐Intermediated Pathway Boosts CO ₂ Hydrogenation to Aromatics

Abstract

ABSTRACT The rational design of highly efficient catalysts and the development of novel reaction pathways are eternal themes and central challenges in the field of chemical synthesis. Here, we design a dual‐engine catalytic system for CO 2 hydrogenation to aromatics via a synergistic C 2+ alcohols/olefins pathway. The dual‐engine catalytic system initiated by FeCo active sites and CuZnAl promoters guarantees the continuous C 2+ alcohols/olefins supply, delivering a record‐breaking aromatics yield (31.1%) with the aid of aromatization component H‐ZSM‐5. Multiple characterization and theoretical simulations reveal that C 2+ alcohols trigger carbon‐chain growth through oxonium‐mediated rapid carbocation generation via a low‐barrier “protonation‐dehydration” sequence, whereas olefins serve as π‐substrates to propagate carbon‐chain. This synergy accelerates both oligomerization and subsequent aromatization, effectively circumventing both the sluggish initial C─C coupling of methanol‐mediated pathways and the high‐barrier direct protonation step in olefins‐mediated pathways. Techno‐economic analysis (TEA) further demonstrates the superior industrial viability of this novel process. This work establishes a new paradigm for designing efficient catalytic systems and engineering process toward sustainable CO 2 valorization.