A Synergistic C₂₊ Alcohols/Olefins-Intermediated Pathway Boosts CO₂ Hydrogenation to Aromatics

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 CO₂ hydrogenation to aromatics via a synergistic C₂₊ alcohols/olefins pathway. The dual-engine catalytic system initiated by FeCo active sites and CuZnAl promoters guarantees the continuous C₂₊ 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 C₂₊ 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 CO₂ valorization.