Synthesis of liquid fuel via direct hydrogenation of CO₂

Synthesis of liquid fuels (C₅₊ hydrocarbons) via CO₂ hydrogenation is very promising. Hydrogenation of CO₂ to liquid hydrocarbons usually proceeds through tandem catalysis of reverse water gas shift (RWGS) reaction to produce CO, and subsequent CO hydrogenation to hydrocarbons via Fischer-Tropsch synthesis (FTS). CO₂ is a thermodynamically stable and chemically inert molecule, and RWGS reaction is endothermic and needs a higher temperature, whereas FTS reaction is exothermic and is thermodynamically favored at a lower temperature. Therefore, the reported technologies have some obvious drawbacks, such as high temperature, low selectivity, and use of complex catalysts. Herein we discovered that a simple Co₆/MnO_x nanocatalyst could efficiently catalyze CO₂ hydrogenation. The reaction proceeded at 200 °C, which is much lower than those reported so far. The selectivity of liquid hydrocarbon (C₅ to C₂₆, mostly n-paraffin) in total product could reach 53.2 C-mol%, which is among the highest reported to date. Interestingly, CO was hardly detectable during the reaction. The in situ Fourier transform infrared characterization and ¹³CO labeling test confirmed that the reaction was not via CO, accounting for the eminent catalytic results. This report represents significant progress in CO₂ chemistry and CO₂ transformation.