Decoupling of Reaction Network for Ultra‐High Yield Synthesis of Olefins From CO 2 Hydrogenation Over Fe‐Based Catalysts

Fe‐based catalysts are promising for CO 2 hydrogenation to olefins. However, the sluggish C═O bond activation and undesirable H 2 O oxidation of iron carbide are central challenges that induce an activity‐selectivity trade‐off. In this study, we present a reaction network decoupling strategy to tackle these obstacles, in which γ‐Al 2 O 3 acts as a commander to trigger the initial C═O bond activation, as well as tailoring the H 2 O‐related microenvironment. Multiple characterizations combined with theoretical calculations reveal that with the aid of surface oxygen vacancies and hydroxyl, γ‐Al 2 O 3 bypasses the high‐energy barrier step (CO 2 * → HCOO*) that originally driven by the Fe‐based sites. Meanwhile, the intrinsic hydrophilicity of γ‐Al 2 O 3 constructs H 2 O diffusion channels to perfectly avoid the undesirable H 2 O‐oxidation phenomenon. This completely novel strategy boosts an unprecedented olefins space‐time yield of 3323.1 mg/g cat /h. The process simulation verifies its industrial application potential. This work sheds new light on the rational design of catalytic systems for C1 molecules conversion and beyond.