Selectivity control is ac hallenging goal in Fischer-Tropsch (FT) synthesis.H ydrogenolysis is knownt oo ccur during FT synthesis,b ut its impact on product selectivity has been overlooked. Demonstrated herein is that effective control of hydrogenolysis by using mesoporous zeolite Y-supported cobalt nanoparticles can enhance the diesel fuel selectivity while keeping methane selectivity low. The sizes of the cobalt particles and mesopores are key factors whichd etermine the selectivity both in FT synthesis and in hydrogenolysis of nhexadecane,amodel compound of heavier hydrocarbons.The diesel fuel selectivity in FT synthesis can reach 60 %with aCH 4 selectivity of 5% over aN a-type mesoporous Y-supported cobalt catalyst with medium mean sizes of 8.4 nm (Co particles) and 15 nm (mesopores). These findings offer an ew strategy to tune the product selectivity and possible interpretations of the effect of cobalt particle sizea nd the effect of support pore sizei nF Tsynthesis.Fischer-Tropsch (FT) synthesis,aprocess for the conversion of syngas (CO/H 2 )d erived from nonpetroleum carbon resources such as natural gas (also shale gas), coal, and biomass,i nto hydrocarbon fuels and chemicals,h as received renewed interest because of the growing global demand for liquid fuels and the depletion of petroleum. Extensive studies have been devoted to developing efficient catalysts for FT synthesis, [1] but the effective control of product selectivity remains one of the grand challenges.T he FT products generally follow the Anderson-Schulz-Flory (ASF) distribution, which is unselective for the middle-distillate products. [1b] Fore xample,t he selectivities of products in gasoline (C 5-11 ) and diesel (C 10-20 )f ractions are limited to 45 and 39 %, respectively.Conventionally,the FT products are subjected to further hydrotreatment to increase liquid fuel selectivity. Compared to this two-stage process,the direct production of specific-range liquid fuels would be more energy and cost efficient.Recently,bifunctional FT catalysts,which combine either ruthenium, cobalt, or iron nanoparticles for CO hydrogenation, and acid sites in az eolite like H-ZSM-5 for hydrocracking,h ave been harnessed to enhance the C 5-11 selectivity. [2,3] However,few studies have succeeded in the direct and selective production of C 10-20 hydrocarbons, [4] even though the FT-based diesel fuel is known to possess many advantages such as low sulfur and aromatic content, and reduced NO x and particulate matter emissions. [5] Herein, we report an ew strategy to improve the C 10-20 selectivity by effective control of hydrogenolysis.We expected that the use of zeolite H-Y,having aweaker Brønsted acidity than H-ZSM-5, might cause milder hydrocracking of heavier primary hydrocarbons formed on FT metals and lead to higher C 10-20 selectivity.H owever,the Co/ H-Y catalyst did not show enhanced C 10-20 selectivity compared to that of Co/SiO 2 and Co/Al 2 O 3 ,w hich are two conventional FT catalysts,b ut its C 21+ selectivity was lower because of the Brønsted a...