Effect of Structure on the Catalytic Performance of 2D and 3D Hierarchical Porous Fe‐Based Catalysts for Fischer–Tropsch Synthesis

Fischer–Tropsch synthesis (FTS) is a green and sustainable technology that enables the direct conversion of biomass‐derived syngas (CO and H 2 ) into gasoline range fuels. Fe‐based bifunctional catalysts have attracted significant attention from researchers owing to their excellent catalytic performance. However, the influence of reaction space regulated by catalyst morphology and crystal growth orientation on FTS catalytic performance remains insufficiently investigated. In this study, two types of hierarchical porous catalysts with distinct morphologies (2D disc‐like and 3D cubic‐like) were fabricated. The effect of crystal growth orientation on catalytic performance was explored by adjusting the hydrothermal reaction time. In this work, ZSM‐24 was physically mixed with 3D cubic‐like catalyst and 2D disc‐like catalyst, respectively. The corresponding bifunctional catalysts were denoted as FeZ and FedZ. It was found that FeZ‐2 and FeZ‐10 with a comparable preferred orientation between (104) plane and (110) plane provide an excellent C 5 –C 11 selectivity of 64.6 and 62.9 wt%. In comparison with the 2D structured FedZ‐10 catalyst, the 3D structured FeZ‐10 catalyst is more suitable for the transportation of syngas and products during FTS. Thus, the FedZ‐10 catalyst only achieves a CO conversion of 43.7%. In contrast, the 3D structured FeZ‐10 catalyst with a larger reaction space exhibits a high CO conversion of 93.6% along with excellent selectivity toward the target gasoline range products. This phenomenon is attributed to the fact that the catalyst structure not only affects the transformation of iron oxides into active iron carbides but also determines the mass transfer space for FTS products, thereby influencing the catalytic performance.