Water Gas Shift Reaction Catalyzed by Rhodium-Manganese Oxide Cluster Anions

Fundamental understanding of the nature of active sites in real-life water gas shift (WGS) catalysts that can convert CO and H₂O into CO₂ and H₂ 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 Rh₂MnO_1,2^- 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 H₂O 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 Rh₂MnO_1,2^- is paramount for the generation of an electron-rich Mn⁺-Rh^- bond that is critical to capture and reduce H₂O and giving rise to a polarized Rh⁺-Rh^- bond that functions as the real redox center to drive the WGS reaction.