Decoupling of Reaction Network for Ultra‐High Yield Synthesis of Olefins From CO 2 Hydrogenation Over Fe‐Based Catalysts
Zhiang Yuan, Qi Li, Dingyao Li, Yang Wang, Jian Wei, Zhongquan Xiang, Song Li, Kaixuan Huo, Xinze Bi, Qiang Liu, Jian Sun, Noritatsu Tsubaki, Mingbo WuABSTRACT
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.