Guo Lisheng, Gao Xinhua, Gao Weizhe, Wu Hao, Wang Xianbiao, Sun Song, Wei Yuxue, Kugue Yasuharu, Guo Xiaoyu, Sun Jian, Tsubaki Noritatsu
School of Chemistry and Chemical Engineering, Anhui University Hefei Anhui 230601 China
State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University Yinchuan 750021 PR China.
Chem Sci. 2022 Nov 16;14(1):171-178. doi: 10.1039/d2sc05047a. eCollection 2022 Dec 21.
Catalytic conversion of CO to long-chain hydrocarbons with high activity and selectivity is appealing but hugely challenging. For conventional bifunctional catalysts with zeolite, poor coordination among catalytic activity, CO selectivity and target product selectivity often limit the long-chain hydrocarbon yield. Herein, we constructed a singly cobalt-modified iron-based catalyst achieving 57.8% C selectivity at a CO conversion of 50.2%. The C yield reaches 26.7%, which is a record-breaking value. Co promotes the reduction and strengthens the interaction between raw CO molecules and iron species. In addition to the carbide mechanism path, the existence of CoFe sites can also provide sufficient O-containing intermediate species (CO*, HCOO*, CO *, and ) for subsequent chain propagation reaction the oxygenate mechanism path. Reinforced cascade reactions between the reverse water gas shift (RWGS) reaction and chain propagation are achieved. The improved catalytic performance indicates that the KZFe-5.0Co catalyst could be an ideal candidate for industrial CO hydrogenation catalysts in the future.
将一氧化碳催化转化为具有高活性和选择性的长链烃具有吸引力，但极具挑战性。对于传统的含沸石双功能催化剂，催化活性、一氧化碳选择性和目标产物选择性之间的不良配位常常限制长链烃的产率。在此，我们构建了一种单钴改性的铁基催化剂，在一氧化碳转化率为50.2%时实现了57.8%的碳选择性。碳产率达到26.7%，这是一个破纪录的值。钴促进了还原过程，并增强了原料一氧化碳分子与铁物种之间的相互作用。除了碳化物机理路径外，钴铁位点的存在还可以为后续的链增长反应（即含氧物机理路径）提供足够的含氧化合物中间物种（CO*、HCOO*、CO*等）。实现了逆水煤气变换（RWGS）反应与链增长之间增强的级联反应。改进后的催化性能表明，KZFe-5.0Co催化剂可能是未来工业一氧化碳加氢催化剂的理想候选者。
