Selective Conversion of Carbon Dioxide into Liquid Hydrocarbons and Long-Chain α-Olefins over Fe-Amorphous AlOx Bifunctional Catalysts

Considerable progress has been made in the conversion of carbon dioxide (CO 2 ), which is highly thermodynamically stable, into liquid hydrocarbons using metal oxide/zeolite composite catalysts. Nevertheless, producing liquid hydrocarbons with a single catalyst without utilizing additional C–C coupling agents remains a formidable challenge. Herein, we report a bifunctional iron aluminum oxide (FeAlO x ) catalyst that directly converts CO 2 into C 5+ hydrocarbons with an overall selectivity of 77.0% and CO 2 conversion of 20.2% at a H 2 /CO 2 ratio of 1:1. Notably, the selectivity for linear α-olefins (LAOs) was 52.4%, accounting for 78.4% of the total C 4+ olefins. At a high H 2 /CO 2 ratio of 3:1, the yield of C 5+ hydrocarbons was 19.7%. The concept of crystalline-/amorphous-structured active sites in the single FeAlO x catalyst was proposed. The reducible magnetite (Fe 3 O 4 ) phase, which contains surface oxygen vacancies, facilitated the reverse-water–gas-shift (RWGS) reaction to form CO via CO 2 hydrogenation, and subsequent C–C coupling over Hägg iron carbide afforded lower olefins (C 2 –C 4 = ). Long-chain LAOs were then formed on the surface of amorphous aluminum oxide (AlO x ) via the readsorption of C 2 –C 4 = . In addition, the amorphous AlO x phase enhanced CO 2 and H 2 adsorption, which facilitated the formation of carbonate, bicarbonate, and formate species via the RWGS reaction and the subsequent formation of long-chain hydrocarbons via the Fischer–Tropsch reaction. The bifunctional FeAlO x catalyst showed excellent stability for up to 450 h on-stream, demonstrating its potential as a practical-scale catalyst for the conversion of CO 2 into value-added liquid fuels and chemicals.