The direct production of liquid fuels from CO₂ hydrogenation has attracted enormous interest for its significant roles in mitigating CO₂ emissions and reducing dependence on petrochemicals. Here we report a highly efficient, stable and multifunctional Na–Fe₃O₄/HZSM-5 catalyst, which can directly convert CO₂ to gasoline-range (C₅–C₁₁) hydrocarbons with selectivity up to 78% of all hydrocarbons while only 4% methane at a CO₂ conversion of 22% under industrial relevant conditions. It is achieved by a multifunctional catalyst providing three types of active sites (Fe₃O₄, Fe₅C₂ and acid sites), which cooperatively catalyse a tandem reaction. More significantly, the appropriate proximity of three types of active sites plays a crucial role in the successive and synergetic catalytic conversion of CO₂ to gasoline. The multifunctional catalyst, exhibiting a remarkable stability for 1,000 h on stream, definitely has the potential to be a promising industrial catalyst for CO₂ utilization to liquid fuels.

This review covers recent developments in the synthesis of α-olefins and aromatics from CO ₂ hydrogenation via direct and indirect routes.

Na-containing Fe₃O₄ nanocatalysts show improved performance in CO₂ hydrogenation due to enhanced surface basicity and carburization induced by residual Na.