Chen Jiao-Jiao, Li Xiao-Na, Liu Qing-Yu, Wei Gong-Ping, Yang Yuan, Li Zi-Yu, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center of Excellence in Molecular Sciences, Beijing 100190, China.
J Phys Chem Lett. 2021 Sep 9;12(35):8513-8520. doi: 10.1021/acs.jpclett.1c02267. Epub 2021 Aug 31.
Fundamental understanding of the nature of active sites in real-life water gas shift (WGS) catalysts that can convert CO and HO into CO and H is crucial to engineer related catalysts performing under ambient conditions. Herein, we identified that the WGS reaction can be, in principle, catalyzed by rhodium-manganese oxide clusters RhMnO in the gas phase at room temperature. This is the first example of the construction of such a potential catalysis in cluster science because it is challenging to discover clusters that can abstract the oxygen from HO and then supply the anchored oxygen to oxidize CO. The WGS reaction was characterized by mass spectrometry, photoelectron spectroscopy, and quantum-chemical calculations. The coordinated oxygen in RhMnO is paramount for the generation of an electron-rich Mn-Rh bond that is critical to capture and reduce HO and giving rise to a polarized Rh-Rh bond that functions as the real redox center to drive the WGS reaction.
深入了解实际应用的水煤气变换（WGS）催化剂中活性位点的本质，对于设计能在环境条件下运行的相关催化剂至关重要，该催化剂可将CO和H₂O转化为CO₂和H₂。在此，我们确定水煤气变换反应原则上可在室温下由气相中的铑 - 锰氧化物簇RhMnO催化。这是簇科学中构建此类潜在催化作用的首个实例，因为发现能够从H₂O中夺取氧并随后提供锚定氧以氧化CO的簇具有挑战性。水煤气变换反应通过质谱、光电子能谱和量子化学计算进行了表征。RhMnO中的配位氧对于生成富电子的Mn - Rh键至关重要，该键对于捕获和还原H₂O以及产生极化的Rh - Rh键起着关键作用，而极化的Rh - Rh键作为驱动水煤气变换反应的真正氧化还原中心发挥作用。
