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.

In this work, we explore the catalytic application of atomically monodisperse, thiolate-protected Au 25 (SR) 18 (where R = CH 2 CH 2 Ph) nanoclusters supported on oxides for CO oxidation.The solution phase nanoclusters were directly deposited onto various oxide supports (including TiO 2 , CeO 2 , and Fe 2 O 3 ), and the as-prepared catalysts were evaluated for the CO oxidation reaction in a fixed bed reactor. The supports exhibited a strong effect, and the Au 25 (SR) 18 /CeO 2 catalyst was found to be much more active than the others. Interestingly, O 2 pretreatment of the catalyst at 150 °C for 1.5 h significantly enhanced the catalytic activity. Since this pretreatment temperature is well below the thiolate desorption temperature (∼200 °C), the thiolate ligands should remain on the Au 25 cluster surface, indicating that the CO oxidation reaction is catalyzed by intact Au 25 (SR) 18 /CeO 2 . We further found that increasing the O 2 pretreatment temperature to 250 °C (above the thiolate desorption temperature) did not lead to any further increase in activity at all reaction temperatures from room temperature to 100 °C. These results are in striking contrast with the common thought that surface thiolates must be removed ; as is often done in the literature work ; before the catalyst can exert high catalytic activity. The 150 °C O 2pretreated Au 25 (SR) 18 /CeO 2 catalyst offers ∼94% CO conversion at 80 °C and ∼100% conversion at 100 °C. The effect of water vapor on the catalytic performance is also investigated. Our results imply that the perimeter sites of the interface of Au 25 (SR) 18 /CeO 2 should be the active centers.The intact structure of the Au 25 (SR) 18 catalyst in the CO oxidation process allows one to gain mechanistic insight into the catalytic reaction.