Catalytic CO Oxidation by O 2 Mediated with Single Gold Atom Doped Titanium Oxide Cluster Anions AuTi 2 O 4–6 −

Gas‐phase studies on catalytic CO oxidation by O 2 mediated with gold‐containing heteronuclear metal oxide clusters are vital to obtain the structure−reactivity relationship of supported gold catalysts, while it is challenging to trigger the reactivity of clusters with closed‐shell electronic structure in O 2 activation. Herein, we identified that CO oxidation by O 2 can be catalyzed by the AuTi 2 O 4–6 − clusters, among which AuTi 2 O 4 − with closed‐shell electronic structure can effectively activate O 2 . The reactions were characterized by mass spectrometry and quantum chemical calculations. Theoretical calculations showed that in the initial stage of O 2 activation, the Ti 2 O 4 moiety in AuTi 2 O 4 − contributes dominantly to activate O 2 into superoxide (O 2 − ⋅) without participation of the Au atom. In subsequent steps, the intimate charge transfer interaction between Au and the Ti 2 O 4 moiety drives the direct dissociation of the O 2 − ⋅ unit.